Vacuum 59 (2000) 845}853

DC electric-"eld e!ect in bulk and thin-"lm Ge As Te

  
chalcogenide glass
A. Abdel-All *, A. Elsha"e
, M.M. Elhawary

Physics Department, Faculty of Science, Helwan University, Cairo, Egypt

Physics Department, Faculty of Science, El-Menouxa University, Shebin El-Koom, Egypt

Abstract

The electrical properties of Ge As Te have been carried out as a function of temperature at di!erent dc
  
electric "elds for the bulk and thin "lms. This material shows a non-ohmic behaviour by switching to
a negative resistance state. The activation energy was found to decrease slowly as the electric "eld increases
and increases again before switching to the negative region. The conduction is simply a "eld-dependent
hopping mobility at low "elds. The high-"eld conduction mechanisms have been explained in terms of the
Poole}Frenkel e!ect and Schottky emission of carriers which is applicable to both bulk and thin
"lms.  2000 Elsevier Science Ltd. All rights reserved.

Keywords: Chalcogenide; Switching; Electric "eld

1. Introduction

Many studies have been made on the switching phenomena in chalcogenide glasses and the
cause of the switching phenomena has been classi"ed into those initiated thermally [1,2] and those
initiated electronically [3,4]. Ovshinsky [5] discussed the major features of switching phenomena
in Te As Si Ge . Mehra et al. [6] reported the thermally initiated switching characteristic in
   
bulk Se-Te-Ge systems. They found that < 's are very sensitive to the ambient temperature of the

sample. Amorphous chalcogenide alloys were the most investigated materials which exhibit the
phenomenon of threshold switching [7]. The detailed experimental observations of switching in
chalcogenides can be explained by the valence alternation pair (VAP) model [8,9]. Nearly all the
successful measurements have been made using glasses containing a relatively high percentage of

* Corresponding author.

0042-207X/00/$ - see front matter  2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 2 - 2 0 7 X ( 0 0 ) 0 0 3 7 8 - X
846 A. Abdel-All et al. / Vacuum 59 (2000) 845}853

As and Te. The ability to observe a measurable "eld e!ect depends critically on the time constants
for carrier trapping. It also leads to the suggestion of the existence of a predominant VAP in these
materials [10,11].
We will show that a careful analysis of the e!ect of temperature and electric "eld on the electrical
measurements can help interpret the conduction mechanisms.

2. Experimental

In order to investigate the "eld e!ect in chalcogenide glasses experimentally, we chose a ternary
alloy of Ge As Te . The amorphous samples of Ge As Te were prepared by mixing the
     
appropriate elements in an evacuated silica tube (10\ Torr) heated to 10003C for 12 h and the melt
was then quenched in iced water. Details of the preparation have been given elsewhere [12]. The
absence of peaks in the X-ray patterns were obtained by an XD-3 di!ractometer showing the
amorphicity of such composition.
Samples in the form of small thin #akes +1 mm and thin "lms were used for the present work.
The bulk sample was placed on a thin copper plate and a platinum probe attached to a very light
pressure spring was used in contact with the top surface to maintain consistent contact pressure.
The current}voltage characteristics and the electrical resistance at di!erent electric "eld values
were carried out as a function of temperature. For measurements at higher temperatures, the whole
sample holder was placed in a thermostatically controlled oven. The current was measured using
a series standard resistance (100 )) using a Keithley electrometer 610C and the voltage was
monitored using a null detector Keithley electrometer 155. Thin "lms with thickness 0.1 lm were
deposited on glass substrates and two silver electrodes with 0.1 cm separation were deposited on
the "lm surface. Gap structure thin "lm samples were prepared on glass substrates with a pre-
deposited Au electrode (1 mm wide and 1 lm thick) and with a gap of 0.2 mm held at room
temperature in a vacuum level of the order of 10\ Torr.

3. Results

The typical I}< characteristics on the surface with coplanar electrodes for thin "lms of 0.1 cm
electrode separation at 295 K are shown in Fig. 1. The I}< curves exhibit an ohmic, nonlinear and
negative resistance behaviour as the electric "eld increases. The subsequent switching cycles tend to
lower the resistance and < decreases reaching stable values. It is noticed that the resistance of the

device at voltage values below < is higher than that after more cycles.

A series of measurements on the I}< characteristics at di!erent ambient temperatures is shown
in Fig. 2 for bulk samples with 0.1 cm thickness. The value of < at the turn over point decreases,

while the value of I increases with increasing temperature. In the negative resistance state

(negative region), the current value for all ambient temperatures becomes close to the same value at
the end of the negative region, indicating that the total current is dominated by the current passing
through a small cross-sectional area between the two electrodes.
Figs. 3 and 4 show the resistance as a function of temperature at several electric "elds in
the o! state and the negative region for the bulk samples. The activation energy E spectrum
0
 A. Abdel-All et al. / Vacuum 59 (2000) 845}853 847

Fig. 1. The cyclic I}< characteristics of thin "lm sample at room temperature.

Fig. 2. I}< characteristics of the bulk sample at various ambient temperatures.

corresponding to resistance is found to obey the relation:

R"R e#0 /k¹. (1)

The activation energy E is found to increase slightly as the "eld increases. However, above
0
threshold, i.e. in the negative region, E decreases as the electric "eld across the sample decreases
0
(Table 1).
848 A. Abdel-All et al. / Vacuum 59 (2000) 845}853

Fig. 3. The Arrhenius plot of ln R versus 1/¹ in the o! state at di!erent electric "elds.

Fig. 4. The Arrhenius plot of ln R versus 1/¹ in the negative region at di!erent electric "elds.

The I}< characteristics for gap structure thin "lms (0.2 mm electrode separation) carried out at
di!erent ambient temperatures is shown in Fig. 5. A similar behaviour as for bulk samples is
observed. From the relation of ln R against l/¹ in the o! state, (Fig. 6), the activation energy at
di!erent electric "elds has been calculated. Dependence of the dc resistance on high "eld was
observed, the activation energy slightly increases as the electric "eld increases [13] (Table 1). The
 A. Abdel-All et al. / Vacuum 59 (2000) 845}853 849

Table 1
The activation energy in the o! state as a function of electric "eld for bulk and thin "lm devices

Bulk samples Thin "lm samples

O! state Negative region O! state

F (V/m) Energy (eV) F (V/m) Energy (eV) F (V/m) Energy (eV)

25000 0.363 90000 0.396 10000 0.527

32000 0.388 80000 0.273 20000 0.533
40000 0.419 70000 0.212 25000 0.614
50000 0.453 60000 0.178
60000 0.455

Fig. 5. I}< characteristics of the thin "lm at various ambient temperatures.

higher values of the activation energy for the thin "lm show that the "lm resistance is highly
sensitive to the applied electric "eld. The negative region in thin "lms does not conform closely to
that given in Fig. 2, and it may be associated with a rise in temperature on the top surface. This rise
in devices with poor heat sinking is due to Joule heating but in those with good heat sinking, the
switching to the on-state must be an electronic e!ect.
Plot of ln I versus F where I is the current and F is the applied electric "eld is shown in Fig. 7.
The slopes of the straight lines are consistent with a current "eld dependence of the form [14]
Ia exp (bF/k¹). (2)
The qualitative result is evident; as the electric "eld increases, the electric resistance decreases
and the samples exhibit a high "eld behaviour both in bulk and in thin "lms [15].
850 A. Abdel-All et al. / Vacuum 59 (2000) 845}853

Fig. 6. The Arrhenius plot of ln R versus 1/¹ in the o! state at di!erent electric "elds.

Fig. 7. The plot of ln I versus (F).

4. Discussion

Along the o! state I increases as F increases and, at the turn over point, the incremental
resistance of the device is zero, r"d</dI"0. We considered that while in lone-pair materials the
spins were paired and all bonds satis"ed, there would be, in some regions, charge imbalance and
 A. Abdel-All et al. / Vacuum 59 (2000) 845}853 851

polarization from the lone pairs' interaction with nearest neighbours [16]. The dipoles restricted
a displacement or orientation, but, at the turnover point, heat dissipates (due to joule heating and
charge carrier avalanche) and the orientation of dipoles can move easy as the resistance of the
medium is reduced. Due to the accumulation of opposite charges along the negative region, the
dipoles neutralize some of the charges at the turn over point, hence, reducing < as the number of

runs increases (Fig. 1). Also they set up an electric "eld which opposes and therefore reduces the
impressed "eld across the sample thus lowering the potential di!erence. Therefore, the application
of high "elds may polarize the electron clouds of the atoms and the atoms with broken bonds.
There can be structural rearrangements in the direction of the "elds that may a!ect the density of
states in the valence and conduction bands [17,18]. As the current increases, the formation of
a "lament is initiated, which is simply a preferred path for easy generation and movement of
carriers between the two opposite electrodes. Also, in this case the entire current path between the
electrodes heats up, since the heat #ows perpendicular to the current instead of toward the
electrodes. Once a "lament is formed, it will not be completely destroyed even after the current is
reduced to zero. In other words, only part of the "lament returns to the amorphous state (low
conductivity). Within the negative region, the incremental resistance of the device is negative and
the current decreases with increasing ¹ at all values of electric "eld and the device behaves as
a metallic one. The decrease of the activation energy along the negative region may be attributed to
the increase of the thermal stability which, in turn, depends on Joule heating that becomes highly
e!ective. At the end of the negative region, the current increases sharply and its value becomes
slightly dependent on both temperature and electric "eld, signalling the formation of the on-state.
Therefore, on increasing the ambient temperature, the system approaches the chemically ordered
state with lower free energy and this will reduce the amount of the Joule heating required for the
"lament path formation [19].
The switching is thus thought to be due to the following mechanisms:
(a) The linear ohmic part of the I}< curves is in accordance with the thermally assisting hopping
mechanism between the nearest neighbours. The "lament temperature increases very slowly
according to the low thermal conductivity perpendicular to the conductive path.
(b) At the beginning of the nonlinear part, the conductivity is activated by hopping and the
"lament temperature begins to increase until the carriers can be excited beyond the mobility edges
into extended states [20] and

 
E !E
p"p exp ! ! D , (3)
 k¹

where p is the minimum metallic conductivity, E is the mobility edge (the lower level of the
 
conduction band) and E is the equilibrium Fermi level.

The linear behaviour of ln I vs F (Fig. 7) could be interpreted as either Poole-Frenkel [21] or
Schottky [22] emission and these are useful as a guide to the conduction mechanisms in our glassy
samples. The sample switched before the higher "eld regions were reached. We can postulate that
emission from the contacts reaches a maximum at some value of applied "eld, whereupon bulk
conduction increases. This shows that a Schottkys or Poole}Frenkel [23] type of emission is
occurring in these glassy systems and could possibly explain the high "eld behaviour in the o! state
with a considerable similarity to that of bulk As Se glass [24,25]. There is a strong evidence [26],
 
852 A. Abdel-All et al. / Vacuum 59 (2000) 845}853

that the "eld dependence in the chalcogenide glasses shows an exponential variation down to the
lowest measurable "elds. This is due to the mobility edge and the probability of Schottky emission
at internal barriers. Marshall and Miller [27] observe a "eld-dependent mobility in a range of
chalcogenide glasses, which extends down to low "elds of &10 V/cm or less.
In the presence of an electric "eld the carriers acquire energy from the "eld and lose it to phonons
by emitting more phonons than are absorbed. As the "eld increases, the average energy of the
carriers also increases, and the e!ective temperature ¹ is higher than the lattice temperature

¹ [23]. Also the e!ective temperature detected by the Marianer and Shklovskii [28] model showed
that it is "eld dependent. Therefore trapping and recombination of the excess carriers created by
the applied "eld heats the material around ¹ and the device switches to the negative region. Due

to the high density of defects, the transport properties are dominated by the interaction of carriers
with the localized states in the mobility gap for the bulk samples [29]. It appears that the
crystallization rate is enhanced by the bond-breaking which necessarily occurs upon creation of
excess carriers. It is possible that the new VAP's which are induced further enhance the rate of
crystallization.

5. Conclusion

The electrical transport in such chalcogenide glass can be explained by free carrier band motion
or by hopping between localized states. Threshold switching behaviour is based on strong "eld
emission and the formation of Schottky barriers at both electrodes. The electro-thermal switching
mechanism is basic in both bulk and thin-"lm devices. In thin "lms, the inhomogeneity of
conductivity and "eld will a!ect the behaviour close to the threshold point. As can be seen,
a memory e!ect is present which could "nd practical application in Ovonic (switching) type devices
and in hermetic integrated circuits.

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