Journal of the Korean Physical Society, Vol. 51, No. 2, August 2007, pp.

664∼668

Trap-Controlled Space-Charge-Limited Current Conduction in the Cr-Doped

SrTiO3 Thin Films Deposited by Using Pulsed Laser Deposition

Bach Thang Phan, Chulho Jung, Taekjib Choi and Jaichan Lee∗
School of Materials Science and Engineering, Sungkyunkwan University, Suwon 440-746

(Received 9 November 2006)

Current-voltage (I-V) characteristics of 0.2 % Cr-doped SrTiO3 (Cr-STO) thin film in a metal-
insulator-metal (MIM), i.e., Pt/Cr-STO/La0.5 Sr0.5 CoO3 , structure were measured, and the elec-
trical conduction was investigated. The I-V characteristics exhibited hysteretic and asymmetric
behaviors. The hysteretic behavior is attributed to bistable resistive switching between a high-
resistance state (HRS) and a low-resistance state (LRS) with voltage polarity. The voltages that
induced the resistance switching were above ±3 V. The resistance ratio between the two conduction
states was about two orders of magnitude. An analysis of the I-V characteristics revealed that
the electrical conduction behavior followed a trap-controlled space-charge-limited current. The
trap-filled limit voltage, VT F L , was –1.6 V.

PACS numbers: 84.40.Ik, 84.40.Fe

Keywords: Cr-doped SrTiO3 , MIM structure, Resistance switching, Trap-controlled space-charge-limited
current mechanism.

I. INTRODUCTION hand, the physical mechanism of this resistance switch-

The transition-metal oxides with perovskite struc-
tures, such as titanates, zirconates, and manganites, are
attracting much interest in applications for resistive ran-
dom access memories (ReRAM), because these materials
show reversible resistance switching induced by an exter-
nal bias [1–7]. Several mechanisms have been proposed
for the resistance switching effect, i.e., the carrier trap-
ping/detrapping process, a metallic filamentary path, a
Mott transition, and the electrochemical migration of
oxygen ions. Meijer et al. reported that the insulator-
to-metal transition is accompanied by an increase in the
valence of the Cr underneath the anode from Cr3+ to
approximately Cr4+ [3]. Odagawa et al. suggested that
the collective nature in the trap-filling and trap-defilling
processes due to strong electron correlation may play a
key role [4].
The transition-metal oxides include perovskite oxides,
such as SrTiO3 , and the binary oxides, such as NiO and
TiO2 , as good candidate materials for applications to
the resistive random access memories. SrTiO3 is a typ-
ical perovskite oxide with a band gap of 3.2 eV and ex-
hibits a wide range of the transport properties from in-
sulator to conductor and even superconductivity upon
doping with various elements. By appropriate composi-
tional doping, one can transform the insulating state of
SrTiO3 to a conducting state, such as La1−x Srx TiO3 ,
SrTi1−x Nbx O3 , and SrTiO3−δ [8–11]. On the other
∗ E-mail: jclee@skku.edu; Fax: +82-31-290-7410
-664-
ing effect is quite unclear at present. Since electrical con-
duction is closely related to the switching mechanism, in
this study, we have investigated the dependence of the
resistance ratio on the sweep-voltage and the electrical-
conduction behaviors of Cr-doped SrTiO3 thin films.
II. EXPERIMENTS
A 100-nm-thick La0.5 Sr0.5 CoO3 layer (LSCO) was de-
posited as a bottom electrode on single-crystalline (100)-
oriented SrTiO3 substrate, followed by the deposition of
a 0.2 % Cr-doped SrTiO3 (Cr-STO) layer with a thick-
ness of 100 nm. Prior to the deposition, the SrTiO3 (100)
substrate was wet-etched by using an NH4 F-buffered HF
(BHF) solution to obtain a step-and-terrace structure for
an atomically flat surface [12] and subsequently a high-
quality Cr-STO thin films.
The surface topographic features of Cr-STO films
were then investigated by using atomic force microscopy
(AFM). All the deposition processes were carried out
by pulsed laser deposition (PLD, λ = 248 nm, KrF ex-
cimer laser) with an energy density of 2.0 J/cm2 and
a pulse repetition rate of 5 Hz. During the deposition,
the substrate temperature was kept at 650 ◦ C, and the
oxygen pressure was kept at 100 mTorr. After the de-
position, the substrate was then cooled down under an
oxygen pressure of 400 Torr. For the MIM structure,
100-nm-thick Pt top electrodes with various diameters
Trap-Controlled Space-Charge-Limited Current· · · – Bach Thang Phan et al.
Fig. 1. Typical I-V hysteretic curve of Cr-doped SrTiO3
measured at room temperature. The arrows indicate the
sweep direction.
(50, 100, 200 and 300 µm) were defined by using a lift-
off process with photolithography and sputtering. The
current-voltage (I-V) measurement was carried out us-
ing a Keithley 2400 source meter at room temperature.
The voltage profile for the I-V measurement was 0 V →
–Vmax → 0 V → +Vmax → 0 V with Vmax being 1, 2,
3, 4, 5 or 10 V. The positive direction of the bias voltage
corresponded to the positive bias applied to the Pt top
electrode.
III. RESULTS AND DISCUSSION
A typical I-V characteristic of the Pt/Cr-STO/LSCO
structure in the voltage control mode is shown in Fig. 1.
By sweeping the negative bias from 0 to –5 V, the leakage
current suddenly increased at –1.6 V. The negative bias
switched the initial state, a high-resistance state (HRS),
to a low-resistance state (LRS). Subsequently, with the
positive bias from 0 to +5 V, the leakage current sud-
denly decreased above +4 V, resulting in a switching
back to the HRS. The switching from HRS to LRS is
observed only to occur when a negative bias is applied
to the Pt top electrode while the switching from LRS to
HRS is only induced by a positive bias. Therefore, we
believe that the electrical switching in this MIM junc-
tion can be classified as a reversible polarity switching.
The switching behavior leads to a pronounced hysteretic
I-V characteristic with two impedance states, and the
resistance switching is more pronounced in the positive
voltage region. The hysteretic curves were obtained re-
peatedly by sweeping the applied bias. It is noted that
two stable resistance states can be realized because of
the nonvolatility. The resistance ratio between the two
conduction states was about two orders of magnitude.
The hysteretic curve showed the asymmetric behavior
-665-
Fig. 2. I - V characteristics at room temperature repre-
sented as the double-logarithmic I-V plots (a) in the negative
bias region and (b) in the positive bias region.
with the current in the negative voltage region higher
than that in the positive voltage region, which can be
attributed to the different workfunction of the electrodes
in this MIM structure.
The I-V characteristics suggest that different leakage
current mechanisms operate in the negative and the pos-
itive bias regions. To clarify the leakage current mech-
anism, we investigated the I-V characteristics further.
Fig. 2 shows the I-V characteristics represented in a
log I versus log V plot in the negative- (Fig. 2(a)) and
positive-biased regions (Fig. 2(b)). Three distinct re-
gions were observed, and the switching from HRS to LRS
was induced when the negative bias increased from 0 to
–Vmax , as shown in Fig. 2(a). The current was directly
proportional to the applied voltage (I ∝ V) below –1.6
V and varied as I ∝ Vm with m > 2 in the voltage re-
gion from –1.6 V to –3.5 V and m ∼ 2 in the voltage
region above –3.5 V. The current began to increase sud-
denly at a negative threshold voltage of V− T ∼ –1.6 V
(or trap-filled limit voltage VT F L ) with a slope in the
range of 5 – 12. The resistance change of the Cr-STO
-666- Journal of the Korean Physical Society, Vol. 51, No. 2, August 2007
film from the HRS to the LRS was completed at V ∼
2V− T . The Cr-STO film at the HRS exhibited a trap-
controlled space-charge-limited current mechanism, in-
cluding three distinct regions with different slopes, which
corresponds to the Ohm’s law region, the trap-filled-limit
region (TFL) from –1.6 V to –3.5 V, and the trap-free
square-law region above –3.5 V. When the bias voltage
was decreased from –5 V to 0, the leakage current of the
LRS also showed a I ∝ V2 behavior, followed by a linear
behavior (I ∝ V) below –2 V without a sudden decrease
of current. This behavior resulted in the pronounced
hysteresis in the negative voltage region.
The I-V behavior shown in Fig. 2(a) can be modeled
in terms of the space-charge-limited current mechanism
(SCLC) controlled by the trapped charge density [13].
The leakage current at low voltages follows Ohm’s law
expressed by the following equation:
V KT
J = qnµp , (1)
d where β = [ απe0 K∞ ]1/2 and 0 is the permittivity of free
where J is the current density, V the bias voltage, n the
carrier density, µp the mobility of the charge carriers, d
the thickness of the film, q the charge of an electron.
In this region, the density of thermally generated free
carriers inside the thin films is predominant over injected
charge carriers. The sudden increase of the current in
the negative voltage region at V−
T ∼ –1.6 V indicates a
crossover from Ohmic behavior to the trap-filled-limited
conduction. At this voltage, the injected carriers sat-
urate all the trap levels. After the saturation of the all
defects level, additional excess charges appear in the con-
duction band, resulting in a sudden increase of current
with the slope in the range of 5 – 12. Thus, the IVC in
the TFL region is given by the following equation [14]:
2l + 1 l+1 0 r l l V l+1
J = q 1−l µp Nc [ ] [ ][ ], (2)
l+1 Nt l + 1 d2l+1
where l = (Tt /T), Tt being a temperature dependent pa-
rameter characterizing the trap distribution, T the abso-
lute temperature, r is the permittivity of the thin film,
0 the permittivity of free space, Nt the density traps
and Nc the density of states in the conduction band.
The slope in the I-V curve can be used to describe
the distribution of trap levels. A small slope indicates
a gradual distribution while a large slope indicates an
abrupt distribution. With further increases in the ap-
plied voltage, the slope in the TFL region decreased grad-
ually to 2 in the high voltage range, which corresponded
to the trap-free square law, known as Child’s law, with
self-blockage of charge carriers as given by the following
equation:
9 V2
J= 0 r µp 3 , (3)
8 d
In the positive bias scan (i.e., 0 → +5 V → 0) shown
in Fig. 2(b), the I-V characteristics of the LRS show
a linear I ∝ V behavior from 0 to +1.5 V, followed by
a I ∝ V2 behavior before switching to the HRS at the
positive threshold voltage V+T . Once the switching to
the HRS occurred, no sudden change of current was in-
duced by the positive bias. In the + 5 V → 0 sweep,
the I-V characteristics of the HRS showed a power-law
dependence of the current on the voltage with the ex-
ponent being of 2 – 4 above +3 V, followed by a linear
I-V dependence. The I-V characterictics in the positive
bias region can be explained by several reasonable con-
duction mechanisms, such as Schottky-barrier-controlled
conduction, Poole-Frenkel hopping conduction and bulk-
limited space-charge conduction. Firstly, we investigated
the two conductions, Schottky and Poole-Frenkel con-
duction [15]. A typical conduction current dominated by
a Schottky or a Poole-Frenkel mechanism is represented
by the following equation:
Vg
J ∝ exp[βE 1/2 − ], (4)
3
space. K∞ is a high-frequency dielectric constant, and
α is a constant whose value is equal 1 or 4 for the Poole-
Frenkel or the Schottky mechanism, respectively. Vg is
the energy interval between the trap level and the bot-
tom of the conduction band in the case of Poole-Frenkel
conduction or the work-function difference between the
film and the electrodes in Schottky conduction mecha-
nism.
If the conduction current at high electric fields is
governed by Schottky-barrier-controlled conduction or
Poole-Frenkel hopping conduction, the current behavior
will follow a linear relationship in a plot of log J versus
E1/2 , where the high-frequency dielectric constant (K∞
= n2 ) is obtained. The value of n from our experimen-
3
tal data was calculated via β = [ απe0 K∞ ]1/2 , and the
β value was estimated from the slope of the I-V plot.
The value of n was 1.22 and 0.82 corresponding to the
β values of 6.2 × 10−5 eV (m/V)1/2 and 9.2 × 10−5 eV
(m/V)1/2 for the HRS and the LRS, respectively. These
values were different from the reported β values (3.2 ×
10−5 for Poole-Frenkel and 1.6 × 10−5 eV (m/V)1/2 for
Schottky conduction), which correspond to an n value
of 2.4 [16], although the current (log J) depends on the
electric field (E1/2 )in a typical Poole-Frenkel or Schottky
mechanism. Furthermore, we investigated the tempera-
ture dependence of the current from 100 K to 410 K. The
temperature dependence of the refractive index n did not
follow the typical behavior of the Schottky nor the Poole-
Frenkel mechanism. Therefore, the leakage current in the
positive bias region is not dominated by the Schottky or
the Poole-Frenkel conduction mechanism. Finally, the
power m in the range of 2 – 4 from the I-V characterictic
(I ∝ Vm ) suggests the onset of a space-charge-limited
conduction.
A similar electrical conduction behavior was also ob-
served for Cr-doped SZO [1], Pr0.7 Ca0.3 MnO3 (PCMO)
[4], La0.7 Ca0.3 MnO3 [14], Ba0.5 Sr0.5 TiO3 [17], Ce-
doped Ba0.5 Sr0.5 TiO3 [18] and Co-doped Ba0.5 Sr0.5 TiO3
Trap-Controlled Space-Charge-Limited Current· · · – Bach Thang Phan et al.
Fig. 3. I - V characteristics measured at various sweep
voltages represented as the double-logarithmic I-V plots (a)
in the negative bias region and (b) in the positive bias region.
The bias voltage was swept in the sequence 0 V → –Vmax →
0 V → +Vmax → 0 V. Different values of ±Vmax were used in
the measurements. The arrows indicate the sweep directions.
[19]. Odagawa et al. described resistance switch-
ing in a PCMO film with a Ag top electrode by us-
ing trap-controlled space-charge-limited current through
an Ohmic contact [4]. A Au/Ba0.5 Sr0.5 TiO3 /Pt ca-
pacitor showed a space-charge-limited current behav-
ior when the Au electrode was biased negatively [17].
Wang et al. reported that Ba0.5 Sr0.5 TiO3 also ex-
hibited a space-charge-limited-current behavior when
Ba0.5 Sr0.5 TiO3 was doped with Ce or Co [18, 19]. The
leakage current mechanism in both the positive and the
negative bias regions was a bulk-limited mechanism, in-
cluding trap or defect sites. In our Pt/Cr-STO/LSCO
structure, those defects could be impurities having dif-
ferent oxidation states and vacancies located in the band
gap at various levels, such as oxygen vacancies, Cr or Ti,
which may be formed in the deposition process.
To investigate further the dependence of the resistance
switching on the sweep voltage, we examined the influ-
ence of the sweep voltage by measuring I-V curves at
-667-
Fig. 4. Resistance-ratio with sweep voltage (a) in the neg-
ative bias region and (b) in the positive bias region.
different sweep ranges. Fig. 3(a) shows that the I-V
curves had no hysteretic behavior for –Vmax (the maxi-
mum voltage of the negative sweep voltage) smaller than
–3 V. When –Vmax was larger than –3 V, a hysteretic
behavior was observed. As mentioned above, the HRS
will be switched into the LRS under a negative sweep
voltage at –Vmax > 2V− T because all trap sites are fully
filled above this value (i.e., –3 V). The injected carrier
density increases with further increase in the negative
sweep voltage (–Vmax ) up to –10 V, and injected trapped
carriers remain after removing the negative bias until a
positive threshold voltage of V+ T is applied, resulting in
pronounced hysteretic curves in the negative voltage re-
gion. Similar to the negative voltage region, no hysteretic
behavior was observed in the positive voltage region for
+Vmax (the maximum voltage of positive sweep voltage)
smaller than +3 V, as shown in Fig. 3(b). A hysteretic
behavior was also observed when +Vmax was larger than
+3 V. The positive threshold voltage V+ T for switching
from the LRS to the HRS was also above +3 V and was
proportional to –Vmax . V+ T increased with increasing –
Vmax . It is also noted that the current at the HRS was
insensitive to ±Vmax while the current at the LRS de-
pended strongly on –Vmax , as shown in Fig. 3. Since
the leakage current at the LRS is controlled by trap-free
space-charge-limited conduction, the current at the LRS
is immediately influenced by the injected carriers, whose
density depends on –Vmax . On the other hand, the leak-
age current at the HRS is dominated by trap-controlled
space-charge-limited conduction, which leads to a cur-
rent insensitive to the sweep voltage.
Fig. 4 illustrates the dependence of resistance ratio on
the sweep voltage. The resistance switching is negligible
below the maximum sweep voltage (Vmax ) of ±3 V and
increased significantly up to 102 at ±10 V. Therefore,
sweep voltages larger than ±3 V are needed to obtain a
significant resistance ratio in this structure.
-668-
IV. CONCLUSIONS
We have investigated electrical conduction mechanism
of the Pt/0.2 % Cr-doped SrTiO3 /La0.5 Sr0.5 CoO3 struc-
ture. The current-voltage characteristics showed hys-
teretic and asymmetric behaviors. The resistance switch-
ing showed a polarity dependence, and the switching
voltage was above ±3 V. The HRS was insensitive to
±Vmax while the LRS depended strongly on –Vmax . The
resistance ratio between the two conduction states was
about two orders of magnitude. The electrical conduc-
tion mechanism exhibited a trap-controlled space-charge-
limited current. The trap-filled limit voltage, VT F L , was
–1.6 V.
ACKNOWLEDGMENTS
This study was supported by the National Research
Program for the 0.1-Terabit Non-Volatile Memory Devel-
opment sponsored by the Korea Ministry of Commerce,
Industry and Energy and by the Korea Science and Engi-
neering Foundation (KOSEF) through the National Re-
search Lab (NRL) program (M10400000364).
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