3-2: A.C Conductivity. 3-2.0: Introduction.: T Do D

‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬
3-2: A.C CONDUCTIVITY.
3-2.0: Introduction.
Consider the application of an alternating electric field

E , E  Eo cos  t , across a dielectric material, the orientation of any
dipoles which are present, will lag behind the applied field. So, the
electric displacement current
D  Do cos ( t   ) , (3.17)
where  = lag phase angle.
D  Do cos  cos  t  Do sin  sin  t (3.18)
This leads us to define two dielectric constants
Do cos  Do sin 
`  &  ``  (3.19)
o Eo o Eo
linked by the relation

 ``
`
 tan  (3.20)
It is convenient to combine these two quantities into a complex

dielectric constant or relative permittivity
    `  j  `` ; j  1 (3.21)
The meaning of the real and imaginary parts may be readily
appreciated by considering the material in a capacitor (capacitance Co
when empty). The current (I) which flows in the external circuit after
application of an alternating voltage [V  Vo exp ( j t ) ] , may be calculated
as follows:
dv dv
IC   Co   Co ( j  t )
dt dt
  Co ( ``  j  ` ) V
This implies that we have a capacitive component of the current,
‫( ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬46)‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬
I c  j  Co  ` V , (3.23)
which leads the voltage by 90°, and a resistive component,
I R   Co  `` V , (3.24)
which is in phase with the voltage.
The basic theory of dielectric relaxation behavior, pioneered by

Debye [38], begins with a macroscopic treatment of frequency
dependence. This treatment rests on two essential principals
i) The exponential approach to equilibrium,
ii) The applicability of the superposition principle.
According to Debye's theory, the dispersion equation,
d D(t ) d D (t )
  D (t )    o     o  S E (t ) (3.25)
dt dt
have the solution

D (t )   
  ( )     S (3.26)
 o E (t ) 1 j 
S  
or  ` ( )     (3.27)
12 2
S  
 `` ( )   (3.28)
12  2
The graphs of  ` and  `` against frequency of the applied field

(logarithmic scale) through the dispersion region are shown in Fig. (8).
The dielectric loss peak has a half-height width of 1.14 decades. The
maximum loss value occurs when    1 , corresponding to a critical
frequency  p  1 /  , and location of this peak provides the easiest way of
obtaining the relaxation time from experimental results. If we eliminate
the parameter (  ) between equations (3.27) and (3.28), we obtain:
2 2
 `  S      
      S  
``2
(3.29)
 2   2 
‫‪  S   ‬‬ ‫‪ ‬‬
‫‪This is the equation of a circle, with center, at ‬‬ ‫‪, 0 ,‬‬ ‫‪and of radius‬‬
‫‪‬‬ ‫‪2‬‬ ‫‪ ‬‬
‫‪ S   ‬‬
‫‪‬‬ ‫‪.‬‬ ‫‪So that a plot of‬‬ ‫‪ `` against  ` should‬‬ ‫‪given a semicircle, as‬‬
‫‪ 2‬‬ ‫‪‬‬
‫‪shown in Fig. (9).‬‬
‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ)‪ (48‬ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬
‫)‪Fig. (8‬‬
‫‪Deoye dielectric dispersion curves.‬‬
‫‪Relaxations observed in amorphous materials, show broader‬‬
‫‪dispersion curves and lower loss maximum than those predicted by the‬‬
‫‪Debye model, and the curve falls inside the semicircle. This led Cole‬‬
‫‪and Cole [39] to suggest the following semiempirical equation for‬‬
‫‪dielectric relaxations.‬‬
S  
     , 0  1 (3.30)
1  ( j   )1
where  denotes the angle of tilt of the circular arc from the real axis,
this equation (3.30) better describes a broad dispersion, and gives a
[ ``   ` ] -plot where the center of the semicircle is depressed below the
abscissa. It corresponds to a superposition of a group of Debye - like

relaxation processes with a range of relaxation times that are
symmetrically distributed about .
3-2.1: Dielectric relaxation in solids

Several distinct dielectric relaxation processes are usually present in
a solid materials. This is seen most easily in a scan of dielectric loss at
constant frequency as a function of temperature, Fig. (10). As the
temperature is raised, molecular mobilities of various types become
successively energized and available for dipolar orientations. Goldstein
[40] have predicted the presence of "island of mobility" in which local
rearrangements is possible, but long-rang flow is impossible. This theory
can explain the weak secondary relaxation (  -relaxation) which
observed at temperatures below glass-transition temperature Tg.
In general, we can consider that at a critical temperature (Tcrit) a

structural change, (the  to a transition), from the more "solid-like"
below (Tcrit) to the more "liquid-like" above (Tcrit) can take place.
‫)‪Fig. (9‬‬
‫‪Semicircular Cole-Cole plot‬‬
‫)‪Fig. (10‬‬
‫‪A schematic dielectric loss curve‬‬
‫‪3-2.2: The A.C Conductivity in amorphous semi conductors.‬‬
‫‪There are three mechanisms of charge transport that can contribute‬‬

‫‪to a direct current in amorphous semiconductors. They can all contribute‬‬
‫‪to the a.c. conductivity as follows.‬‬
3-2.2 (a). Transport by carriers excited to the extended states near
Ec or Ev.
For these we might expect that  ( ) would be given by a formula
of the Drude type,
 ( 0)
 ( )  (3.31)
1   2 2
The time of relaxation  will be very short (~ 1015 Sec.) and a

decrease in  ( ) as  2 is not expected until a frequency ~ 10 Hz is 15
reached. It is sufficient to state here that in the electrical range of

frequencies (up to, 107Hz) no frequency dependence of the conductivity
associated with carriers in extended states is expected.
3-2.2 (b). Transport by carriers excited into the localized states at

the edges of the valence or conduction band.
No complete theoretical treatments of  ( ) for hopping under
condition of non-degenerate statistics are known, but we might expect a
similar dependence on frequency to that derived under degenerate
condition [3-2.2(c).] and thus as  S , where S < 1 when    ph . The
temperature dependence of the a.c. conductivity should be the same as
that of the carrier concentration at the band edge, so that for the
conduction band it should increase as:
exp [- (EA-ET) /kT].
3-2.2 (c). Hopping transport by electrons with energies near the

Fermi level, N(Ef) is finite.
There have been several theoretical treatments of  ( ) for this mode
of conduction.  ( ) should increase with frequency in a manner similar
to that for process [3-2.2(b)]. However, the exponential dependence on
the temperature will be absent, and  ( ) should be proportional to T.If
(kT) is small compared with the energy range over which N(Ef) may be
taken as constant, and independent of T if (kT) is larger than the width
of some well-defined defect band in which Ef lies.
The analysis of observed results has been given by Mott and Davis
[37], using the formula given by Austin and Mott [41], namely:
4
    ph 
 ( )    e 2 kT  N ( Ef ) 2   5  n   (3.32)
3    
This analysis also have been discussed by Pollak [42] and by

Butcher [43] and they obtained a similar formula with a slightly
   3 
  [42]
different numerical factor, replacing   in
3
eq. (3.32) by or
 96 
 3.66 2 
  [43].
 6 
The frequency dependence predicted by equation (3.32) can be

written as  ( )   S , where s is a weak function of    ph , and
considering that:
d [n { n 4 ( ph /  )}]
S
d (n  )
(3.33)
4
1
n ( ph /  )
A schematical illustration of the frequency dependence of the

conductivity expected for the three conduction mechanisms is shown in
Fig. (11). For the two hopping process, [3-2.2(b)] and [3-2.2(c)],  ( )
increases as  S . A distinction between the a.c conductivity processes (b)
and (c) can be made by observing their temperature dependencies.
‫)‪Fig. (11‬‬
‫‪Schematic illustration of the frequency dependence of conductivity‬‬
‫‪for the three modes of conduction‬‬
Fig (12) Elliot, Model.

Which, concider the hopping of carrier between two sites
and tunneling through the barier.
Elliott [44, 45] has proposed a model for the mechanism responsible
for a.c conductivity in chalcogenides which overcomes most of the
problems associated with interpretation in terms of the Austin-Mott
formula [41]. The model considers hopping of carriers between two sites
over a barrier separating them, rather than tunneling through the barrier
Fig. (12, a, b). On this model the a.c conductivity can be represented by
6
 2 N 2 o   8 e2   S
 ( )     (3.34)
24   o WM  ( o)
where:
6 KT
S 1  ,  (3.35)
WM
o   the effective dielectric constant

WM (  E o  2  E ) the binding energy, (e.v)
Eo is the optical band gap

 E is the electrical activation energy
N is the concentration of localized sites, (cm 3 )
According to this model, s is predicted to have a temperature
dependence proportional to T and the magnitude of s at any temperature
is determined by the binding energy of the carrier in its localized site. A
connection between the a.c conductivity and the d.c. conductivity is
predicted for these materials where, WM  2 ( Eo  E ) .Values of N
deduced, according to this model, from data on arsenic chalcogenides
and Se lie between 1.8 x 1018 and 2.2 x 1019 cm-3, which have values
similar to those deduced from other measurements.
Elliott also has pointed out that in "IVAP" state, Intimate Valence
Alternation Pairs, (i.e R. 1  1 ) the energy required to remove an
electron from its site to the conduction band is (  W ) ,which can be
1
calculated if (n  p ) is plotted versus ( )
T
,where:
W (3.36)
n ( p )  n (o) 
KT
The value for WM is expected to be  4 W
‫)‪CHAPTER (IV‬‬
‫‪SWITCH I NG AND MEMORY PHENOMENA‬‬
‫‪4-1‬‬ ‫‪: THEORETICAL MODELS FOR SWITCHING AND‬‬

‫‪MEMORY PHENOMENA.‬‬
‫‪4-1.0‬‬ ‫‪: Introduction.‬‬
‫‪4-1.1‬‬ ‫‪: Thermal Induced Crystallization.‬‬
‫‪4-1.2‬‬ ‫‪: Thermal switching mechanism.‬‬
‫‪4-1.3‬‬ ‫‪: Electronic Mechanism.‬‬
‫‪4-1.3(a). : Double injection‬‬
‫‪4-1.3(b). : Recombinative injection.‬‬
‫‪4-1.3(c). : Impact ionization.‬‬
‫‪4-1.4‬‬ ‫‪: The electro-thermal Theory.‬‬
4-2 : FACTORS AFFECTING ON SWITCHING AND
MEMORY PROCESS.
4-2.1 : Dependence of Threshold Voltage on Sample Thickness.
4-2.2 : Effect of Uniaxial Pressure.
4-2.3 : Effect of Composition and Temperature on Threshold
Voltage.
4-1: THEORETICAL MODELS FOR SWITCHING AND

MEMORY PHENOMENA.
4-1.0: Introduction.
Chalcogenide glass switches are normally classified into "threshold"

(or monostable) and "memory" (or bi-stable) devices. The first
references of switching in chalcogenide glasses were reported 30 years
age [46], but ovshinsky's paper of 1968 [4] probably marked the point at
which the subject became of serious interest in solid-state electronics.
The switching process observed in amorphous semiconductors is

characterized not only by the breakdown of the high resistance state of
the material but very importantly by the presence of a positive feedback
mechanism which provide the high conductance ON-state so that the
breakdown nondestructive and repetitive switching is possible.
Generally, switching may be interpreted on any mechanisms based on
the shift of the Fermi level or band edge toward each other.
The various models proposed to explain the switching process may

be categorized into:
4-1.1:Thermal Induced Crystallization

Stocker [47], proposed a model for switching and memory effect
based on thermally induced crystallization. The threshold switching
action takes place in a small region somewhere along a crystalline path.
Application of voltage pulses can move this region to different position
and is shown to be equivalent to memory switching. Surface temperature
measurements showed that high temperature exists in this localized
region. After such a forming process the device usually exhibit a lower
threshold voltage Vth, and a lower off resistance than the virginal device
[48, 49, 50]. At the same large change in the I-V characteristics of the
off state are observed. All evidence suggests that the forming process
creates in the filament region a new material whose properties have little
relation to those of' the original material. Bosnell and Thomas [49] were
able to isolate the filament region of the formed devices and they
suggest that "The large change of the material properties in the filament
region are associated with phase separation and partial crystallization".
Pearson [11] studied switching and memory effects in As.Te.I

system. He explained the memory effect by phase change rnechanism.
Passing high current in the switch results in enough Joule heating to
allow phase change to occur. The new phase which is crystalline has a
high conductivity and extends continuously between the electrodes.
Then this will form a conducting path which will be stable at zero bias.
The passage of critically large current pulse in the memory state, results
in the fusion of hot spots, along its path. If the current is stopped
abruptly, this fused regions would be quenched to the glassy state.
The models proposed for explanation of fast threshold switching is
qualitative and has the following features:
(1) After application of the electric field, heating produces local
devitrification. Once nucleated, it proceeds extremely rapidly,
possibly at the speed of sound and produces a filamentary path of
devitrified material.
(2) The current increases further until a limit determined either by the
external circuit or the resistance of the structure is reached. The
filamentary path consists now of molten material at high
temperature.
(3) Upon reduction of the current, cooling results in transformation of
the molten filament into the glassy state. The cooling rate must
be fast enough so that the transformation to the glassy state rather
than phase separation, occurs.
4-1.2: Thermal switching mechanism.
The most popular model for switching in chalcogenide glasses.

especially those whose resistivity decreases rapidly with increasing
temperature is that of thermal runaway. Ovshinsky and Fritzche [51]
indicated that thermal breakdown is caused by joule self-heating of the
material. After applying of the bias voltage, the temperature in the
glassy material rises until a critical temperature is reached. The result is
formation of a thermal filament. At serious thermal effects are present
the I-V curve can show an appreciable pre-switching region of negative
differential resistance as found in thermistors, associated with
measurable temperature rise on the top surface of the [52].
From results it was found that if no significant, heating of the

electrodes occurs, a virtual electrode or and a field-dependent
conductivity is required for negative resistance or switching and
negative resistance is always accompanied by high-current filament,
formation. Results of the calculation for the thermal model also showed
the threshold voltage has a square root dependence on sample thickness
at large thickness and a linear-dependence at small thickness.
4-1.3: Electronic Mechanism.

Because of the large field enhancement of the conductivity before
breakdown one suspects the electric processes such as carrier avalanche,
double injection, or high field tunneling can initiate a breakdown
process before the thermal or electro thermal breakdown proceeds.
4-1.3(a).Double injection
Double injection and trap limited space charge saturation may occur
when carriers are injected by emission at the electrodes. These carriers
are utilized to fill traps. When all traps are filled at saturation the Fermi
level is shifted completely into the neighboring conduction or valence
band. Then additional carriers will unimpeded producing the switching
transition and the low-resistance region. Applying a strong electric field
produces extra carrier concentrations. Then the Fermi level splits into
two quasi-Fermi levels, one near the conduction band and the other near
the valence band, producing charge neutrality in most of the
interelectrode gap of the material and leaving the potential drop at the
electrodes. In the double-injection model the carriers injected at the
electrodes have equivalent effects and result in space-charge neutrality
where the space-charge clouds overlap [53].
4-1.3(b). Recombinative injection.

Recombinative injection is a minority-carrier, space charge
injection, which produces an injected region of near-zero net local
recombination. The injection can occur in relaxation semiconductors;
which are specified by a dielectric relaxation time greater than the
diffusion-length lifetime at thermal equilibrium, such injection of
electrons is reported to cause switching in the amorphous case, after all
majority holes have been activated from centers by the field [54]. The
theory [54] describes the amorphous alloys as types of minimum-
conductivity (p-type) relaxation semiconductors as a result of
pronounced recombination. In their post-switching on state, there is a net
space charge between electrodes, and the potential drop is mostly near
the anode in a narrow recombination front.. This has a low differential
resistance because in it carriers are kept. Activated by a field equal the
threshold field when bias is sufficient to maintain the on-state.
4-1.3(c). Impact ionization.
Impact ionization is an electronic switching mechanism where by

carriers which are accelerated by the field cause ionization that in turn
releases more carriers for energy transport [55].
4-1.4: The electro-thermal Theory.

This theory takes into account the field-dependent conductivity of
the active material, space charges and current injection by the electrodes.
In many chalcogenides the high field region of  can often be expresses
by [56].
  C exp (  E / KT ) exp ( F / Fo ) (4.1)
or by
  C exp (  E  e F S / 2 ) KT (4.2)
where Fo is in the order of 2.5×104 V/cm which is nearly 5 percent of
the field at threshold and S  200 A . o
So many types of electronic and thermal processes have been

proposed to explain the mechanism of threshold switching on the other
hand, the memory effect appears to be due to a thermal process. In all
cases, there is a current filament for both the switching and the memory
effect i.e. the current is conducted through filament.
4-2: FACTORS AFFECTING ON SWITCHING AND MEMORY

PROCESS.
It was shown earlier that amorphous semiconductors display
memory and switching phenomena. In this section, a review of some
factors affecting these characteristics such as temperature. composition,
uniaxial pressure and samples thickness are given.
4-2.1: Dependence of- Threshold Voltage on Sample Thickness.

Kolomiets, et.al [57] measured the dependence of the firing field
upon sample thickness in the region 0.3-1000 microns. In thick layers
the firing field decreases with increasing thickness as expected for
thermal breakdown where as in thin films up to about 8 microns, the
firing field is almost constant. These results show considerable evidence
that switching in thick films is caused by thermal break-down.
4-2.2: Effect of Uniaxial Pressure.

The strain energy produced by applying pressure to a sample may
produce the same effect as thermal heating. Actually, the strain energy
affects the conduction process in two ways.
(1) The strain energy in some cases is capable to rise the temperature of
the filament region by a value T . Thus the temperature of the
conduction bath is higher that the rest of the sample. Consequently,
the observed decrease in (Vth) as the uniaxial pressure increases is in
fact due to the raise in temperature of the strained region due to
induced thermal strain energy.
(2) The average distance between the atoms in the strained region may
changes by increasing the uniaxial pressure. This may lead to a
change in the dispersion curve (E-K). This in turn cause a change in
the band structure of the strained region. So, the activation energy
of the conduction process undergoes a change according to the
topology of the top and the bottom of the valence and conduction
bands.
4-2.3: Effect of Composition and Temperature on Threshold

Voltage.
Okada, et.al [58] observed that the value of threshold voltage in

As.Te.Ge glasses increases as the concentration of As increase. It is
interesting to note that Savage [59], showed that the glass transition
temperature increase as the concentration is increased and hence
crystallization becomes difficult. Thus the threshold voltage increases as
the glass transition temperature increase.
The effect of temperature was studied by Bunton [60]. He observed

that the relation between log Vth / T Vs 1 / T is not linear for As.Te.Ge.Si
thin films of low thicknesses. But for films of thicknesses greater than
10  m , the dependence of Vth / T on1 / T became linear and of activation
energy 0.33 eV. which was approximately half the activation energy of
the material 0.6 eV. This showed that results on thick films are in
agreement with the thermal model. The switching action in thin films is
complex and may involve electronic mechanism.
Tanaka, et.al [61], studied the temperature dependence of the

threshold voltage for switching in amorphous materials in the
As(x)Te(y).Ge(10) and As(x) Te(y) Si(10) systems. They observed that
the threshold voltage measured for various compositions of the material
decreases exponentially as a function of temperature. They deduced a
simple experimental relationship Vth = k.exp [c.(Tg–T)]; where Vth is the
dc. threshold voltage for switching and Tg is the glass transition
‫‪temperature. The constant k takes different values for each system, while‬‬
‫‪constant c has the same value in both systems.‬‬
‫‪Theses results indicate that the switching phenomena in bulk‬‬

‫‪chalcogenide amorphous material is intimately related not only to‬‬
‫‪thermal effects but also to the bond energy of strong chemical bonding‬‬
‫‪covalently formed by Ge or Si.‬‬
‫]‪CHAPTER [V‬‬
‫‪LITERATURE REVIEW OF PREVIOUS‬‬

‫‪WORK ON CHALCOGENIDES‬‬
‫‪5-1‬‬ ‫‪: FILAMENT FORMATION AND ITS TEMPERATURE.‬‬

‫‪5-2‬‬ ‫‪: SOME PREVIOUS WORK ON CHALCOGENIDES.‬‬
‫‪5-3‬‬ ‫‪: AIM OF THE WORK.‬‬
5-1: FILAMENT FORMATION AND ITS TEMPERATURE.
In the present chapter we will review some observation on filament

formation as an Introduction to our Filament temperature Model All
switching mechanism models suggests the presence of a current
filament. Uttecht et.al [62l, carried a cinematographic study of the
filament formation between two point probes on the surface of bulk
sample of As 55. Te 35. Ge 10. The following sequence was recorded.
(1) When the dc voltage applied across the probes on the surface of the
sample, reached a certain threshold value, a process initiate on a line
joining the probes them travel outward. This process is characterized
by a decrease in the electrica1 resistance and a change in the surface
reflectively. This decreased resistance persists as long as certain
minimum current is maintained otherwise the resistance reverted to
its original high value.
(2) If the applied dc voltage is maintained a filament will grow out of the
anode and terminate at the cathode. The filament growth rate depend
on the applied voltage. When the filament growth is complete the
low resistance will remain if the applied voltage is removed.
(3) There are two possible ways to revert back to the high resistance
state. First by gradually increasing the dc applied voltage through a
small current limiting resistance until visible melting of the filament
occurs. A more suitable disordering of the filament occurs if a
narrow voltage pulse of sufficient energy is applied. In this manner
the high resistance state can be restored without any observable
disruption of the filament. This type of reversal probably transforms
only the narrowest portion of the filament back to the high resistance
state.
Stocker [47] added the following observations during the filament
formation:
(1) A sharp click can often be heard as the path forms.
(2) The formation of the path appears to be not thermal and once
initiated proceeds at an extremely rapid rate, possibly the speed of
sound.
(3) The path shows devitrification when examined under the
microscope.
(4) The current-voltage characteristic of the path tend to be rather
unstable but occasionally they can be stable for several hours.
Matsushita [63] reported that the shape of the high current density
path, formed between gold electrodes evaporated on the bulk surface of
As. Te. Ge glass depended on the material composition.
Stocker [47] measured the surface temperature profiles using

infrared microradiometer of thin film device of Si3. Ge6 As33. Te49.
Gu9. He recorded a temperature of 100°c in the middle distance between
the electrodes just before breakdown.
Sie [64], focused a radiometric microscope on a spot midway
between the anode and the cathode. As the applied voltage reached a
threshold value, an abrupt jump both in the current and temperature
traces. The measured temperature reached 320°c. The high temperature
maintained until the advancing filament passes through the spot. The
experiment indicate the exothermic nature of the filament formation and
the good thermal conductivity of the filament relative to that of the
material in front of the filament. The filament growth was not completed
until about 45 sec. after the first abrupt current increase.
Uttecht et. al [62]using electron microprobe analysis to investigate

the filament composition. He observed that inside the filament there was
37.6 wt% increase in Te, 40.8 wt% decrease in As and 47 wt% decrease
in Ge compared to the composition some distance away from the
filament. X-ray diffraction proves that the filament. Path is crystalline.
Sie [64], investigated the composition of the filament grown in
As55. Te35. Ge10 glass. The resultant composition of the filament is
As39 Te57 Ge4. i.e., As and Ge concentration decreases while Te
increases.
Okade et.al [58], classified the glassy region in the ternary As.Ge.Te
phase diagram to two regions. The glassy region I, is the region of high
As concentration and the glassy II is that of lower As concentration.
They determined the composition of the filament of both regions using
microprobe analysis. They found that fro all samples belonging to the
small As concentration region, gives filaments of composition has nearly
the same composition as the original material. But the specimens belong
to region I of high As concentration. The lock ON filament has nearly
the stiochometric composition As2 Te3 in most of the filament. The
filament also has very high Te concentration near the anode and very
high As concentration near the cathode. X-ray structure studies prove
that all the filaments are crystalline.
Johnson [65]. Identified vapor species resulting from electronically

induced threshold switching and memory bulk AS. Te. I and As.Te.Ge
glasses. He found that the common parent species are As4 (more intense)
and Te2.
The results indicated the existence of filaments in memory and

threshold switching. The filament nature is exothermic and its growth
characterized by increase in Te concentration: and decrease in As and
Ge concentration. These filaments are crystalline in nature.
The results of Okade suggested that the filament composition in

glasses of lower As concentration differs from filaments in glass region
of high As concentration. Also it suggested that ionic: motion of the
constituent, elements plays a role in the compositional change during
filament formation, specially in glasses of high As concentration.
Ovshinsky and Fritzsche [51] indicated that thermal breakdown is
caused by Joule self heating of the material. When heat generation
exceeds the cooling term in the heat balance equation, self heating is
generally expected to occur in all materials whose resistivity decreases
rapidly with increasing temperature. The thermal break-down theory is
particularly attractive because it is independent of the detailed
conduction mechanism of the material and on further information is
needed then the heat conduction and capacities, and temperature
dependence of the electrical conductivity.
Chalcogenide glasses are characterized by low thermal conductivity

and an electrical conductivity of the approximate form:
   o exp (  E / 2 KT ) (5.1)
with  o about 103 ohm-1 cm-1 for most amorphous semiconductors with
values of  E 0.6 and 1.5 eV.
The calculation of thermal breakdown requires the solution of the

differential equation
dT
C   E 2  . ( KT ) (5.2)
dt
for temperature T as a function of position and time t, where C is the

specific heat per volume, K is the thermal conductivity and  is the
electrical conductivity. Solution of equation (5.2) can be easily found by
two limiting cases:
(a) Impuls thermal breakdown, equation (5.2) can be approximated by
neglecting the heat conduction term. This is permissible when the
voltage is applied rapidly enough.
(b) Steady state breakdown, i.e., when the current is increased slowly,
allows to neglect the time derivative. The heat conduction term then
balances the Joule heating term.
Although heat is conducted in all directions, two sub cases are
treated.
(i) axial heat flow and
(ii) radial heat f low.
Since only radial heat flow is considered, the current and voltage
scales can easily be changed to apply to different electrodes separations.
This characteristics which show an extended negative differential
resistance region. Some hysteresis is observed when the current is
changed too rapidly for maintaining thermal equilibrium. By using a
small values of load changed resistor RL, such device can be made to
dV
switch along the load line from a point at which RL  
dI
to the point
of intersection of the load line and the I-V curve. In this case of
breakdown voltage Vth decreases rapidly with temperature,
approximately as Vth  1 /  , and the highest internal temperature near
Vth is not much larger than ambient. The temperature at breakdown near
Vth is
To  To (1  2 K To / E ) (5.3)
that is about 15o c above ambient for typical cases.
According to the thermal model (Ovshinsky [51]) A.E.owen [66l

who study the switching characteristics of memory switching from a
chalcogenide glass of composition Ge15 Te 81 S 2 Sb2 thin film. He calculate
the filament temperature by solving the heat transport equation by using
T2 k
T f  T 
E
(5.4)
where Tf  the filament temperature
E  the activation energy
T  the ambient temperature
5-2: SOME PREVIOUS WORK ON CHALCOGENIDES.
Glasses in the Ge  Se  Te system were first obtained by Muir and

Cashman [67]. These glasses were obtained by quenching the melt from
high temperature into: mixture of salt and ice [68], or in air [69] or in ice
water [70]. Makovskaya and Zhukov [71] found that this system has two
vitrification regions. They showed that the glass temperature increases
with increasing the Ge content. They found also that the microhardness
of these glasses depends on the Ge and chalcogen content and its value
is 57-115 kf/mm2.
The glass forming region of the system Ge-Se-Te was investigated

by Noda and Maruno [72], Sarrach et. al [73] and Wieder [74]. Noda
and Maruno found that the glass forming region has two island structure.
GeSe and Te were formed in the samples comprising binary systems
GeSe2-Te. They considered that the structures of the glasses in the
system Ge10Se90-xTex are constructed from partially cross-linked Se-Te
chains with Ge, and that Se in the chain structure is progressively
substituted by Te with increasing Te content. In the system (Se1-zTez)2
the substitution of the Se in the structure of GeSe2 by Te makes possible
to form the glasses. This structure can be described as described as
distorted three-dimensional network structure in which the Se-Te chains
are completely cross-linked with Ge, The glasses with high Te content in
these system have a remarkable tendency towards phase-separation.
D.J. Sarrach et al. and J. Wieder et al. showed that the region of
easy bulk glass formation is limited to alloys containing more than about
50 at % Se with an additional region extending from Ge40 Se60 towards
Ge17T83 which is in reasonable agreement with the observations of
Borisova [75]. Most chalcogen-rich compositions showed a discontinues
increase of heat capacity when they heated through the glass transition
temperature Tg. The Ge-rich compositions, which could only be
prepared as sputtered amorphous films, were invariably characterized by
an irreversible exothermic crystallization process on heating beginning
at the crystallization temperature Tc.
Thermal crystallization of Ge20Se40Te40 sputtered films was studied

by D.J. Sarrach et al. [76]. Their studies showed that the films begin to
crystalline between 140oc and 150oc. The initial crystallization product is
Te. Te and GeSe2 crystals are produced by annealing at 375oc for 30
min.
The rates of thermal crystallization were studied [77] and it was

found that the crystallization proceeds from the surface.The dependence
of resistivety,  , on annealing time (t) was described by    o exp ( ct ) ;
where c is the crystallization rate.
By studying the electrical conduction and DTA, H. Sakai et. Al [78]

found that when germanium is added to the binary Te-Se system, it
contributes to from the strong three dimensional network structure and
increases the glass transition temperature. This is because that Ge is
rather favorable to form covalent bonds with Se and Te.
Investigation of the conducting state of the memory glass

Ge15As4Te81 using NMR measurements [79] showed that the conducting
state contains polycrystalline regions of doped Te. Fritzche and
Ovshinsky identified the formation of Te and Ge Te crystalline upon
annealing the glass Ge15As4Te81 at 280oc.
Several interesting features are observed in DTA measurements [11]

on amorphous samples in the tellurium rich end of the glass formation
region in the Ge-Se-Te system. With increasing germanium and
decreasing tellurium content, the softening temperature Tg, and the first
exothermic crystallization peak Tx increase. For Ge15Se4Se81 and the
adjacent compositions, variables peaks are observed, and a pronounced
endothermic peak is observed followed by exothermic activity. The
melting temperature, Tm is approximately 350oC for all the samples. X-
ray diffraction and conductivity data were obtained on these samples
which annealed at temperature slightly higher than each observed
exothermic peak. The results show that the first exothermic peak
corresponds to the crystallization of tellurium, the subsequent
exothermic peaks involve crystallization of Ge Te [11]
Pearson [11], Kolomiets et„al [81], Ovshinsky [82], and other

investigators, showed that many amorphous semiconductors, in
particular chalcogenide glasses, show an electrically controlled
switching and memory effects. Raising the applied electric field above a
certain value causes the material to jump from low to high conductivity
state in less than 0.5 n.sec.
When the current is then reduced there are two possibilities for the
electrical behavior. In the case of a material that shows only switching
effect, the former low conductivity state returns after the current has
fallen below a certain critical value. In the case of material that shows
memory effect the resulting state depends on the current reduction rate.
The high conductivity state can be maintained through slow reduction
even without current flow, whereas fast reduction leads to the low
conducting state.
The critical current varies depending upon the composition of the

glass being used, the device thickness, the temperature and perhaps other
parameters. The device can be made to switch back from the memory
state to the high resistance (OFF) state by passing through it a pulse of
current again greater than a particular critical value for composition and
geometry, and having a tailing edge.
The negative resistance condition can be obtained by operating the
device using a constant current power supply. Alternatively a series
resistor having large value compared to the OFF-resistance of the device
may also be used to approximate constant current conditions.
Kolomiets and Lebedev [81], reported switching and memory

effects for T1 As (Se, Te)2 glass. In their experiments they used a fine
wire as a point contact to one surface of a thin (20 to 200  m) layer of
glass. The opposite surface of the sample was coated
5-3: AIM OF THE WORK.
The purpose of this work is to study the switching characteristics in

bulk Ge-Te-Se system. Very little information is available in the
literature on switching phenomenon in bulk amorphous materials and
conclusions drawn from the studies in thin films may not necessarily be
applicable to bulk materials. Whether threshold or memory
characteristics are observed is mainly a matter of the composition of
chalcogenide glass. A variety of compositions were studied to
investigate the switching dependence on sample composition, thermal
heating and electrical Joule heating. So, to calculate the filament the
temperature one must know the activation energy (E ) and it's variation
with temperature. So we plan to
(1) Measure the I-V curve for the prepared samples at different ambient
temperature and the effect of thickness and pressure on the I-V curve.
(2) Measure the electrical conductivity at constant current value to
neglect the lode line effect on the I-V curves.
(3) Measure the equivalent circuit for the prepared samples by using the
A.C conductivity.
4) Measure the differential thermal analysis of the prepared samples to
indicate the thermal behavior of these sampless.
‫)‪Fig. (13‬‬
‫‪Glass formation in the Ge-Se-Re system, showing quencing techniques‬‬
‫‪required to produce single-phase amorphous samples. Dots correspond‬‬
‫]‪to compositions successfully prepared [11‬‬
‫)‪Fig. (14‬‬
‫‪The sample holders‬‬
‫)‪CHAPTER (VI‬‬
‫‪EXPERIMENTAL TECHNIQUES OF MEASURE-MENTS‬‬
‫‪6-1‬‬ ‫‪: PREPARATION OF AMORPHOUS Ge-Te-Se SYSTEM.‬‬

‫‪6-2‬‬ ‫‪: D.C. CONDUCTIVITY MEASUREMENTS.‬‬
‫‪6-2.1 : I-V Characteristics measurements.‬‬
‫‪6-2.2 : D.C. Conductivity at constant current.‬‬
‫‪6-3‬‬ ‫‪: A.C. CONDUCTIVITY MEASUREMENTS.‬‬
‫‪6-4‬‬ ‫‪: D.T.A. TECHNIQUE.‬‬
EXPERIMENTAL TECHNIQUES OF MEASUREMENTS
6-1: PREPARATION OF AMORPHOUS Ge-Te-Se SYSTEM.
Present samples were prepared to investigate the threshold

switching in the system GeTeSe, which is according to the phase digram
Fig. (13) reported by Sarrach et, al [73], seems to occur primarily in the
finger extending towards the tellurium-rich corner. So we prepare our
samples in this part of the glass formation region. Our samples can be
represented by the formula Gex Tey Se[100-(x+y)] where [x =18, 21, 24 at,
%] and [y = 62, 65, 68 at %]. The desired proportions of high purity
constituents (99.9999 %) were mixed together in a silica ampoule. The
ampoule was evacuated by using a rotary vacuum pump until the
pressure reach the order 1 10 Torr. The dimension of the ampoule is3
(20 cm long, 1 cm diameter and of wall thickness 2 mm). This ampoule

was heated in a muffle furnace [Heraeus Ks 120] with maximum
temperature of 1200 ± 20oc. Ampoules have been heated for h hours at
temperature 1000 ± 20°c with continuous shaking to ensure good
homogeneity. The ampoules in a horizontal direction are then quenched
in ice-water to ensure constant cooling rate. Samples as a small flakes of
thickness ~ 0.05 cm were produced.
Samples were examined by X-Ray diffractometer [Shimadzu XD-3]

with a copper K radiation (  1.5418 A ) in which the 20 value were 
automatically recorded the lack of any sharp peaks indicating the

amorphous state.
6-2: D.C. CONDUCTIVITY MEASUREMENTS
6-2.1 I-V Characteristics measurements

6-2.1(a) The Sample Holder.
The sample holder demonstrated for these measurements is shown
in Fig. (14). The area of the point contact electrode was estimated from
measuring the electrical conductivity of a Germanium single crystal
sample and it was found to be ~ 4.5  10 cm . 3 z
6-2.1(b)The I-V tracer.

The I-V characteristics of bulk samples were measured on flakes
samples with thicknesses  0.05 cm , to ensure the same amporphousity, at
regular temperature intervals, temperature control unit [type Diqi -Sense
Modal Cole-Palmer with K-type sensor (0 to 850o c) ] was used. The
circuit shown in Fig (15) was used for these measurement which consist
of:
(i) Sweeping unit.

A potentiometer (20 M . ) was connected to the power supply
(HITHKIT - model ip17) and driven by a step motor (U.K-M3). Fig (16)
represents the variation of the output voltage across the sweeping unit
with time. A digital multi meter (ITT Metrix - model 727A) was used
for monitoring the sweeping output voltage.
ii -The circuit.
The sample holder shown in Fig (14) containing the sample was
connected in series with a load resistance to limit the current within the
measuring interval.
(iii)Meters and recorder.
For measuring the current an electrometer (Keithley 610C) was
used, while, an electrometer (Keithley 155 null detector) was used for
measuring the voltage drop across the sample. Theses electrometer act,
as a digital to analog converter. By recording the analog voltage using
the X-Y recorder (Franel-model 3500). The I-V characteristics can be
recorded.
with a colloidal silver. They obtained the I-V characteristic of their

devices by applying positive saw tooth voltage pulses to the point
contact. They saw more than two orders of magnitude change in
resistance when the device switched from the high to the low resistance
state.
Altunyan [83], investigated the properties of thin film diode

structure based on four components (Si-Ge-As-Te) chalcogenide glass.
He observed that different electrode material did not affect the
characteristics. The characteristic is symmetrical in the forward and
inverse direction. Three regions, with different dependence of the
current on the voltage, I  V , I V , and I V were observed. 2 3
Croitoru, et. Al [84] investigated the characteristics of As.Te.Ge.Si.

They found that at high fields, the current-voltage curves show a clear
exponential dependence of the type, I  I exp ( BV / KT ), where o
1/ 2
B  ( q / d ),  is the dielectric constant, d is the electrode separation.

3
Feldman and Gutirrez [85], studied switching in amorphous boron

films. They observed that the current at first is ohmic, then change to V2
dependency and finally just before switching, follows Vn relation where
n is greater than 3. Their results show evidence for charge multiplication
and the current described by the relation I  I exp ( .d ), where  is the o
ionization coefficient and d is the thickness.
‫‪Fig (15) Iv tracer‬‬

‫‪ax : Analog output connected to X-axis of X-Y recorder.‬‬
‫‪ay :Analog output connected to Y-axis of X-Y recorder.‬‬
‫‪RL :Load resistance.‬‬
Fig (16)
The variation of the output voltage across the sweeping unit with time.
Time (sec)
6-2.2:D.C. Conductivity at constant current.
Fig (17) represents the circuit diagram used for these measurements
which consist of a current source (Keithley 234 - A) connected to the
sample and the voltage drop across the sample was recorded from the
analogo voltage delivered from the electrometer (Keithley 155 null
detectr). A digital thermometer with analog voltage (1 m.V / 1o c) was
used to record the sample temperature. The heating rate was estimated to
be 3  7 c / min . The chosen current was monitored by using (Keithley
o
616) electrometer.
6-3: A.C. CONDUCTIVITY MEASUREMENTS

The principle of the impedance analysis method is based on
measurements of the sample impedance taken over a wide range of
frequencies and then analyzed in the complex impedance plane.
The impedance analysis method requires the determination of the
real part (Z ) and the imaginary part (Z ) of the impedance Z where,
V ( )
Z  Z . Cos   j Z .Sin  ( )
I ( )
and Z  Z / 2  Z // 2
The Z and  data can be read directly from the impedance meter
used in our experiments at the chosen frequency and the desired
temperature. Hence, the equipment used to determine the complex
impedance is the TESLA BM.507 impedance meter which operates in
the frequency range 5Hz-500k.Hz. The value of Z ranges from
1  to 10 M . and  from  90 to  90 . Theamplitude of the measured signal
o o
varies from3 m.V to 3 V in the resistance range1  to 10 M . .
6-4: D.T.A. TECHNIQUE.

The differential thermal analyzer [Shimadzu DT - 30] was used to
measure the glass transition temperature (Tg), the crystallization
temperature (Tc) and the melting temperature (Tm) in the temperature
range ( 30 - 450 C° ).At various heating rates ranging between 5 and 100
C°/min.
‫)‪Fig (17‬‬
‫‪The circuit diagram used to measure‬‬
‫‪the D.C. conductivity at constant current‬‬

3-2: A.C Conductivity. 3-2.0: Introduction.: T Do D

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3-2: A.C CONDUCTIVITY.

Consider the application of an alternating electric field

linked by the relation

It is convenient to combine these two quantities into a complex

This implies that we have a capacitive component of the current,

The basic theory of dielectric relaxation behavior, pioneered by

have the solution

The graphs of  ` and  `` against frequency of the applied field

abscissa. It corresponds to a superposition of a group of Debye - like

3-2.1: Dielectric relaxation in solids

In general, we can consider that at a critical temperature (Tcrit) a

‫‪There are three mechanisms of charge transport that can contribute‬‬

The time of relaxation  will be very short (~ 1015 Sec.) and a

reached. It is sufficient to state here that in the electrical range of

3-2.2 (b). Transport by carriers excited into the localized states at

3-2.2 (c). Hopping transport by electrons with energies near the

This analysis also have been discussed by Pollak [42] and by

The frequency dependence predicted by equation (3.32) can be

A schematical illustration of the frequency dependence of the

Fig (12) Elliot, Model.

o   the effective dielectric constant

Eo is the optical band gap

N is the concentration of localized sites, (cm 3 )

The value for WM is expected to be  4 W

‫‪SWITCH I NG AND MEMORY PHENOMENA‬‬

‫‪4-1‬‬ ‫‪: THEORETICAL MODELS FOR SWITCHING AND‬‬

4-1: THEORETICAL MODELS FOR SWITCHING AND

Chalcogenide glass switches are normally classified into "threshold"

The switching process observed in amorphous semiconductors is

The various models proposed to explain the switching process may

4-1.1:Thermal Induced Crystallization

Pearson [11] studied switching and memory effects in As.Te.I

The most popular model for switching in chalcogenide glasses.

From results it was found that if no significant, heating of the

4-1.3: Electronic Mechanism.

4-1.3(b). Recombinative injection.

4-1.3(c). Impact ionization.

Impact ionization is an electronic switching mechanism where by

4-1.4: The electro-thermal Theory.

So many types of electronic and thermal processes have been

4-2: FACTORS AFFECTING ON SWITCHING AND MEMORY

4-2.1: Dependence of- Threshold Voltage on Sample Thickness.

4-2.2: Effect of Uniaxial Pressure.

4-2.3: Effect of Composition and Temperature on Threshold

Okada, et.al [58] observed that the value of threshold voltage in

The effect of temperature was studied by Bunton [60]. He observed

Tanaka, et.al [61], studied the temperature dependence of the

‫‪Theses results indicate that the switching phenomena in bulk‬‬

‫‪LITERATURE REVIEW OF PREVIOUS‬‬

‫‪5-1‬‬ ‫‪: FILAMENT FORMATION AND ITS TEMPERATURE.‬‬

5-1: FILAMENT FORMATION AND ITS TEMPERATURE.

In the present chapter we will review some observation on filament

Stocker [47] measured the surface temperature profiles using

Uttecht et. al [62]using electron microprobe analysis to investigate

Johnson [65]. Identified vapor species resulting from electronically

The results indicated the existence of filaments in memory and

The results of Okade suggested that the filament composition in

Chalcogenide glasses are characterized by low thermal conductivity

The calculation of thermal breakdown requires the solution of the

for temperature T as a function of position and time t, where C is the

According to the thermal model (Ovshinsky [51]) A.E.owen [66l

T  the ambient temperature