IEEE ELECTRON DEVICE LETTERS, VOL. 33, NO.

1, JANUARY 2012 11
Resistive Switching in HfO
2
Probed by a
MetalInsulatorSemiconductor Bipolar Transistor
E. Yalon, A. Gavrilov, S. Cohen, D. Mistele, B. Meyler, J. Salzman, and D. Ritter
AbstractResistive switching in thin HfO
2
lms is studied us-
ing a metalinsulatorsemiconductor bipolar transistor structure.
Using this structure, electron injection into the semiconductor va-
lence band can be distinguished from injection into the conduction
band. In addition, the p-n junction serves as a sensitive detector
of damage induced by the switching effect. The implications of the
obtained experimental results on the validity of various conduction
mechanisms through the insulator are discussed.
Index TermsResistive random access memory, resistive
switching (RS), tunneling emitter bipolar transistor.
I. INTRODUCTION
N
EGATIVE resistance in thin oxide insulators was dis-
covered by Hickmott in 1962 [1]. Half a century later,
the closely related resistive switching (RS) effect is a leading
candidate for future resistive memory technology. Success-
ful implementation of the RS effect clearly hinges upon its
proper understanding. However, neither charge transport nor
switching mechanism in most RS devices is well known [2].
Among the many types of resistance-switching oxides, HfO
2
is
an attractive material since it exhibits reproducible switching
characteristics and is already used as a high- dielectric in
silicon technology [3]. In this work, we study the conduction
mechanism in HfO
2
using a metalinsulatorsemiconductor
(MIS) bipolar transistor (MIS-BT). We have recently applied
the MIS-BT technique to study RS in Al
2
O
3
[4]. Here, we
apply the method to HfO
2
-based RS devices, which exhibit
superior switching behavior, and discuss the implications of
our results on the feasibility of possible transport mechanisms
through HfO
2
.
The MIS-BT is composed of a metal emitter that injects
electrons through an insulating layer into the semiconductor
conduction and valence bands. A shorted or backward-biased
p-n junction collects the injected minority carriers as in a
conventional bipolar transistor. The structure is identical to the
tunneling emitter bipolar transistor [5][8], except that electron
injection is not due to direct tunneling. If the injection rate of
Manuscript received September 23, 2011; accepted October 3, 2011. Date of
publication November 3, 2011; date of current version December 23, 2011. This
work was supported in part by the Technion Russell Berrie Nanotechnology
Institute. The review of this letter was arranged by Editor A. Ortiz-Conde.
The authors are with the Department of Electrical Engineering,
TechnionIsrael Institute of Technology, Haifa 32000, Israel (e-mail:
eilamy@techunix.technion.ac.il; arkadiga@ee.technion.ac.il; sscohen@
techunix.technion.ac.il; dmistele@ee.technion.ac.il; meyler@ee.technion.ac.il;
salzman@ee.technion.ac.il; ritter@ee.technion.ac.il).
Color versions of one or more of the gures in this letter are available online
at http://ieeexplore.ieee.org.
Digital Object Identier 10.1109/LED.2011.2171317
Fig. 1. (a) Schematic cross section of the MIS-BT with a p-type base layer.
(b) Energy band diagram of the device at forward bias; electron (I
c
) and hole
(I
b
) current components are indicated. The band gap of InGaAs is 0.74 eV,
the Fermi level is located about 0.12 eV below the valence-band edge at p =
3 10
19
[cm
3
], the band gap of HfO
2
is 5.45 eV, and the band offsets are
E
c
= 1.8 eV and E
v
= 2.9 eV [9].
minority carriers from the metal into the base is larger than the
injection rate of majority carriers into the metal, then current
gain can be achieved [5]. The MIS-BT detects injection into
the valence and conduction bands separately and thus provides
additional information on charge conduction through insulators
that cannot be obtained from metalinsulatormetal (MIM)
devices.
II. EXPERIMENTAL AND DISCUSSION
Fig. 1 shows a cross section and a schematic band diagram
of the MIS-BT. The epitaxial semiconductor stack was grown
by a compact metalorganic molecular beam epitaxy system
[10]. The insulating HfO
2
layers were deposited by atomic
layer deposition. The layer structure of the device is shown in
Table I. The HfO
2
layers were wet etched using HF : H
2
O (1:5)
solution. The metal stack was prepared by the lift-off technique.
The emitter area was 70 80 m
2
. As evident in the band
diagram, electrons injected from the metal emitter into the base
valence and conduction bands constitute the base and collector
0741-3106/$26.00 2011 IEEE
12 IEEE ELECTRON DEVICE LETTERS, VOL. 33, NO. 1, JANUARY 2012
TABLE I
LAYER STRUCTURE OF THE MIS-BT
Fig. 2. Base (hole) and collector (electron) currents versus baseemitter
voltage with a shorted basecollector junction (Gummel plot). Note the simul-
taneous switching of electron and hole currents. The arrows mark the voltage
sweep direction. The inset shows the base current during reset into the HRS.
currents, respectively. Minority carriers that recombine in the
base or at the interface and electrons injected into interface
band-gap states are also detected as base current.
Fig. 2 shows the collector and base currents at positive
base bias. A three- to four-order-of-magnitude set transition
from the high-resistance state (HRS) to the low-resistance state
(LRS) is evident. The most interesting observation is that RS
occurs simultaneously for electron and hole injection [4]. This,
in turn, indicates that the conduction mechanism at the LRS
cannot be of ohmic nature, as further explained in the following.
At the HRS, only charging transients are measured up to about
1 V. At voltages higher than about 1 V, the metal Fermi
level is located above the conduction band, so both base and
collector currents increase exponentially. This behavior implies
that, at the HRS, conduction is due to tunneling (but not direct
tunnelingthe current density is much too high). The inset in
Fig. 2 shows the base current at negative bias where the reset
transition is observed. Only the base current is plotted because
no minority carriers are injected. No additional information is
obtained from these data compared to the data obtained from
conventional MIM structures. Devices with different oxide
thicknesses (5 and 20 nm) were also measured. The behavior
was quite similar for all three thicknesses, except that the set
voltage slightly increased with thickness; moreover, the 20-nm
devices showed less stable switching characteristics, and hard
breakdown of the oxide often occurred prior to forming or set.
In order to avoid damage to the basecollector p-n junction,
we have limited the current during the set transition into the
LRS as shown in Fig. 2. Under these conditions, the measure-
ments are reversible and repeatable. No current compliance
was required at negative bias (the inset in Fig. 2). To obtain
Fig. 3. Base and collector currents at the LRS versus baseemitter voltage
(no current compliance) and current gain = I
c
/I
b
.
Fig. 4. Schematic energy band diagrams of a MIS structure (semiconduc-
tor is heavily doped p-type). Possible current injection paths at (a) low,
(b) intermediate, and (c) high bias levels are illustrated. Electron injection into
interface midgap states and subsequent thermalization into the valence band are
also possible but not indicated.
more insight on the conduction mechanism, we show in Fig. 3
the base and collector currents at the LRS with no current
compliance. At low bias (V
b
< 0.4 V), the electron injection
rate into the conduction band is negligible, and the base current
is due to injection into the valence band, as shown in Fig. 4(a).
At intermediate base bias levels (V
b
0.50.8 V), electrons
are thermally excited to an energy level aligned with the
semiconductor conduction band, where they cross the insulator
as shown schematically in Fig. 4(b). The thermal excitation
rate of the electrons is determined by the Boltzmann statistics,
and the collector current increases as exp(qV/kT) with an
ideality factor of about 1.3, indicating that the tunneling
rate increases with voltage also due to an additional process.
For high base bias (V
b
> 0.8 V), the metal Fermi level is
located above the conduction band, and the current increases
at a lower rate. At high bias, the current is determined by both
the conduction-band density of states and transport through the
insulator [Fig. 4(c)]. The current gain I
c
/I
b
is also plotted in
Fig. 3. The larger-than-unity current gain at bias levels larger
than 1.1 V indicates that, virtually, all electrons are injected
into the conduction band and that the recombination rate at the
dielectricsemiconductor interface is low.
Before discussing the implications of the data on the validity
of previously suggested conduction mechanisms, we briey
comment that, during forming or set without sufciently low
current compliance, the basecollector p-n junction was dam-
aged. No change in the switching behavior of the device (the
YALON et al.: RESISTIVE SWITCHING IN HFO
2
PROBED BY A MIS-BT 13
Fig. 5. (a) Schematic of the conduction mechanism through the oxide sug-
gested in [13] for a discrete impurity level. No collector current is expected.
(b) Schematic of the tunneling between adjacent sites within an impurity band
which may account for the experimental results.
base current) was observed. We conclude from this observation
that the forming and set processes are very energetic, as they
create damage far away from the insulator. This result supports
the lamentary nature of the conduction. Uniform conduction
could not be sufciently energetic to induce damage deep into
the semiconductor. To illustrate this point, we note that our
standard bipolar GaInAs transistors can handle current densities
up to 1 10
6
A/cm
2
. The p-n junction of the MIS-BT was
damaged at 200 A, which implies that the current is most
probably conned to an area smaller than 10
4
nm
2
.
Numerous mechanisms were suggested in the literature to
account for carrier transport in resistance-switching oxides. Our
data rule out conduction through metallic laments connecting
the top electrode and the semiconductor because such laments
should inject the current directly into the valence band (as in
an ohmic contact), and no collector current should have been
detected. However, a localized conducting channel that extends
most of the way across the insulating lm, leaving an insulat-
ing tunneling gap [11], is consistent with our results. In this
case, the applied voltage drops across the tunneling gap, and
electrons are injected directly by tunneling into the conduction
band, as in a tunneling emitter bipolar transistor [5][8]. As
shown in Fig. 5(a), our data also rule out Mott hopping through
trap states [12]: No collector current is expected in this case if
the trap level is located belowthe conduction band, and constant
current gain is expected if the trap level is located above the
conduction band. Moreover, the thermal injection rate into traps
that are located above the conduction band is too low to account
for the large measured current densities.
Another model that may explain our data is tunneling be-
tween adjacent sites within a broad impurity band [14] aligned
as shown in Fig. 5(b). However, a broad localized impurity
band in HfO
2
was not found in ab initio calculations [15]
and is hard to justify theoretically. We nally note that the
similarity of the data reported here to that obtained for RS
in Al
2
O
3
[4] suggests that a general conduction mechanism
exists in thin metal oxides, possibly taking into account 1-D
transport [16].
III. CONCLUSION
A MIS-BT structure was applied to study RS in HfO
2
.
Injection of electrons into the conduction band of the semicon-
ductor through HfO
2
was observed for the rst time. The LRS
conduction model that best explains the results is the formation
of conductive laments that extend through most of the lms,
leaving a small tunneling gap [11].
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