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Emerging memories: Resistive switching mechanisms and current status

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Rep. Prog. Phys. 75 (2012) 076502 (31pp) doi:10.1088/0034-4885/75/7/076502

Emerging memories: resistive switching

mechanisms and current status
Doo Seok Jeong1,6 , Reji Thomas2,6 , R S Katiyar2 , J F Scott3 , H Kohlstedt4 ,
A Petraru4 and Cheol Seong Hwang5
1
Electronic Materials Research Centre, Korea Institute of Science and Technology, Hwarangno 14-gil,
Seongbuk-gu, Seoul 136-791, Republic of Korea
2
Department of Physics and Institute for Functional Nanomaterials, University of Puerto Rico, San Juan,
PO Box 70377, Puerto Rico 00936-8377, USA
3
Cavendish Laboratory, Department of Physics, Cambridge CB3 0HE, UK
4
Nanoelektronik, Technische Fakultät Kiel, Christian-Albrechts-Universität zu Kiel, Kiel 24143,
Germany
5
WCU Hybrid Materials Program, Department of Materials Science and Engineering, and
Inter-university Semiconductor Research Centre, Seoul National University, Seoul 151-744,
Republic of Korea
E-mail: dsjeong@kist.re.kr (Doo Seok Jeong) and etreji@yahoo.com (Reji Thomas)

Received 31 August 2011, in final form 9 April 2012

Published 28 June 2012
Online at stacks.iop.org/RoPP/75/076502

Abstract
The resistance switching behaviour of several materials has recently attracted considerable
attention for its application in non-volatile memory (NVM) devices, popularly described as
resistive random access memories (RRAMs). RRAM is a type of NVM that uses a material(s)
that changes the resistance when a voltage is applied. Resistive switching phenomena have
been observed in many oxides: (i) binary transition metal oxides (TMOs), e.g. TiO2 , Cr2 O3 ,
FeOx and NiO; (ii) perovskite-type complex TMOs that are variously functional, paraelectric,
ferroelectric, multiferroic and magnetic, e.g. (Ba,Sr)TiO3 , Pb(Zr x Ti1−x )O3 , BiFeO3 and
Pr x Ca1−x MnO3 ; (iii) large band gap high-k dielectrics, e.g. Al2 O3 and Gd2 O3 ; (iv) graphene
oxides. In the non-oxide category, higher chalcogenides are front runners, e.g. In2 Se3 and
In2 Te3 . Hence, the number of materials showing this technologically interesting behaviour for
information storage is enormous. Resistive switching in these materials can form the basis for
the next generation of NVM, i.e. RRAM, when current semiconductor memory technology
reaches its limit in terms of density. RRAMs may be the high-density and low-cost NVMs of
the future.
A review on this topic is of importance to focus concentration on the most promising
materials to accelerate application into the semiconductor industry. This review is a small
effort to realize the ambitious goal of RRAMs. Its basic focus is on resistive switching in
various materials with particular emphasis on binary TMOs. It also addresses the current
understanding of resistive switching behaviour. Moreover, a brief comparison between
RRAMs and memristors is included. The review ends with the current status of RRAMs in
terms of stability, scalability and switching speed, which are three important aspects of
integration onto semiconductors.
(Some figures may appear in colour only in the online journal)
6 Authors to whom any correspondence should be addressed.

0034-4885/12/076502+31$88.00 1 © 2012 IOP Publishing Ltd Printed in the UK & the USA
Rep. Prog. Phys. 75 (2012) 076502 D S Jeong et al

Contents
1. Introduction 3 4. Resistive switching materials and mechanisms 15
1.1. Semiconductor memory classification 3 4.1. Resistive switching in oxides 15
1.2. Limitations of the current memory technologies 3 4.2. Higher chalcogenides 18
1.3. Emerging memories 4
2. Basics of resistive switching 6 4.3. Carbon-based materials and other materials 18
2.1. Types of resistive switching 6 4.4. Mechanisms for resistive switching 19
2.2. Resistive switching measurements 7 5. Are RRAMs memristors? 24
3. Electroforming 7 6. Non-volatile memory application 25
3.1. Early mechanisms for electroforming 9 6.1. Scalability of RRAMs 26
3.2. Electrolysis (anodic) reactions and ion or
6.2. Stability of RRAMs 26
ionic defect migration 10
3.3. Resistance change during electroforming 13 6.3. Switching speed of RRAMs 27
3.4. Phase transition 14 7. Concluding remarks and outlook 27
3.5. Electroforming into unipolar or bipolar Acknowledgments 27
switching 14 References 27

Acronyms and symbols OTPROM one-time programmable read-only

memory
PCM phase-change material
PCMO praseodymium calcium manganite:
Acronyms Pr x Ca1−x MnO3
1D1R one-diode and one-resistor PMC programmable metallization cell
1T1C one-transistor and one-capacitor PRAM phase-change random access memory
1T1R one-transistor and one-resistor PTO lead titanate: PbTiO3
AAO anodic aluminium oxide PZT lead zirconate titanate: Pb(Zr x , Ti1−x )O3
BE bottom electrode ROM read-only memory
BFO bismuth ferrite: BiFeO3 RRAM resistive random access memory
BTO barium titanate: BaTiO3 RTJ resistive tunnel junction
CAFM conductive atomic force microscope SBH Schottky barrier height
CD compact disc SBT strontium bismuth tantalite: SrBi2 Ta2 O9
CF conducting filament SCLC space-charge-limited conduction
CMOS complementary-metal–oxide–semiconductor SE solid electrolyte
DRAM dynamic random access memory SRAM static random access memory
DVD digital versatile disc STO strontium titanate: SrTiO3
ECM electrochemical metallization cell STTMRAM spin-transfer torque magnetic
EEPROM electrically erasable read-only memory random access memory
EPIR electric-field-induced resistance change STXM scanning tunnelling x-ray microscope
EPROM erasable programmable read-only memory SZO strontium zirconate: SrZrO3
F minimum feature size TCM thermochemical memory
FRAM ferroelectric random access memory TE top electrode
FTJ ferroelectric tunnel junction TEM transmission electron microscope
FTO iron-doped tin oxide TMO transition metal oxide
HRS high resistance state TOF-SIMS time-of-flight secondary
ITO indium tin oxide ion mass spectrometry
LRS low resistance state UVEPROM ultraviolet erasable programmable
LSCO lanthanum strontium cobalt oxide: read-only memory
Lax Sr 1−x CoO3 VCM valence-change memory
LSMO lanthanum strontium manganite: XANES x-ray absorption near-edge spectroscopy
Lax Sr 1−x MnO3
MFM metal/ferroelectric/metal stack Symbols
MIM metal/insulator/metal stack MOx+δ hyper-stoichiometric compound
MOSFET metal–oxide–semiconductor MOx−δ hypo-stoichiometric compound
field-effect-transistor O×0 oxygen ion on an oxygen ion site,
MR magnetoresistance zero charge (Kröger–Vink notation)
MRAM magnetic random access memory VO·· doubly charged vacancy on an
NVM non-volatile memory oxygen site (Kröger–Vink notation)

2
Rep. Prog. Phys. 75 (2012) 076502 D S Jeong et al
×
MM M ions on an M ion site, zero
charge (Kröger–Vink notation)
Mi·· doubly charged M ion interstitial
(Kröger–Vink notation)
e
electron (Kröger–Vink notation)
e− electron (regular nomenclature)
h· hole
EF Fermi level
EC conduction band edge or minimum
φm work function of metal
V (0) voltage drop through the Helmholtz layer
Evac vacuum level
χTiO2 electron affinity of TiO2
G0f formation free energy at the standard state
Figure 1. Categories of standard semiconductor memories and
emerging memories, e.g. FRAM, MRAM, PRAM and RRAM.
1. Introduction
UVEPROM, all memory cells are simultaneously erased,
1.1. Semiconductor memory classification whereas in an EEPROM memory cells can be erased byte-
or block-wise. A schematic of the semiconductor memory
Sustained advances in integrated circuit technologies
classification is shown in figure 1. Since DRAMs and FLASH
over the past decades have given us computers with
memories constitute the biggest part of the semiconductor
powerful processing capabilities due to high-speed/high-
memory market, we will address the comparison of these
density memories and processors. Additionally, portable
two ‘giants’ and emerging memories that are seriously being
mobile electronic devices are heavily reliant on the
considered to replace the giants in terms of operation speed
development of high-density, high-speed and low-power
and storage density.
memories. Semiconductor memories are classified based on
DRAMs were traditionally used as technology drivers
how many times they can be rewritten into random access
for the semiconductor industry. However, beyond the one
memories (RAMs) and read-only memories (ROMs). In
gigabit generation, FLASH memories have caught up with
RAMs, as the name suggests, information can be written to
DRAMs and now are scaling ahead in terms of storage density
or read from any cells without read/write cycle limitations,
as well as minimum feature size [3]. For a further advance
whereas in ROMs read/write cycles are limited. In RAMs,
of information processing/storage technologies, we need new
writing and reading times are almost the same, whereas in
memory technologies with the possibility of meeting the
ROMs writing takes more time than reading. ROMs are non- integrated circuits’ mottos: small, cheap, fast and reliable.
volatile, that is, the stored information remains even if the A number of alternatives to DRAMs and FLASH memories
power is turned off. have been extensively studied to obtain more powerful
RAMs can be further classified based on the retention and functional memories, so-called emerging memories (see
of the stored information into volatile memories and non- figure 1). The focus of research on emerging memories
volatile memories (NVMs). Volatile memories lose the is on obtaining non-volatile, fast, high-density, low-power
stored information once the power is turned off. Dynamic consumption, high data transfer rate and reliable memories. If
RAMs (DRAMs) and static RAMs (SRAMs) are examples these emerging memories satisfy the positive points of RAMs
of volatile memories. SRAMs are very fast (write/erase and ROMs, then they can be universal future memories.
time: 0.3 ns/0.3 ns) compared with DRAMs (write/erase time:
<10 ns/<10 ns), but the density is very low due to the large
1.2. Limitations of the current memory technologies
unit cell size (six transistors in latched configuration with a
minimum cell size of 140F 2 , where F is the minimum feature FLASH memory is a class of EEPROM, as FLASH memories
size) compared with DRAMs, the unit cell of which is much are also electrically written and erased. However, each
smaller (one-transistor and one-capacitor (1T1C) stack with memory cell in a FLASH memory consists of only one metal–
a minimum cell size of 6F2 ) [1]. Hence, SRAMs are used oxide–semiconductor field-effect-transistor (MOSFET) with
as cache memories where the access time is critical, while an additional floating gate, unlike EEPROMs (two MOSFETs).
DRAMs are used as main memories where the capacity is The operation of FLASH memories is much slower
critical for temporary information storage and processing [2]. (write/erase time; 1 ms/0.1 ms) than DRAMs, and hence they
Depending on reprogrammability, ROMs are classified are used as secondary storage media. The primary limitation
as one-time programmable ROMs (OTPROMs) and erasable of FLASH memories is that while their design is superb
programmable ROMs (EPROMs). OTPROMs, as the name for 5 V operation, there is an international agreement within
suggests, are not reprogrammable, i.e. non-erasable. EPROMs the electronics industry that the standard Si-logic level will
can be erased either by exposing memory cells to ultraviolet decrease from 5 V to 3.3 V to 1.1 V and eventually to 0.5 V in
radiation (ultraviolet EPROMs: UVEPROMs) or by electrical the coming years. FLASH memories (based on the Fowler–
means (electrically erasable PROMs: EEPROMs). In a Nordheim tunnelling) will not reliably function at 0.5 V, and

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Rep. Prog. Phys. 75 (2012) 076502 D S Jeong et al

Table 1. Comparison of conventional and emerging memories. Most data other than those of RRAMs were taken from [1]. RRAMs have
not been demonstrated at the industrial level so some data, e.g. write/erase time and endurance, are of RRAMs at the laboratory level.
Volatile Non-volatile Emerging non-volatile
memory memory memory
Type SRAM DRAM NOR-FLASH NAND-FLASH MRAM PRAM FRAM RRAM
Cell 6T 1T1C 1T 1T 1(2)T1R 1T1R or 1T1C 1T1R or
elements 1D1Ra 1D1Ra
Cell Latch Stack/ Floating Floating Magnetoresistance Phase- Polarization- Resistance-
trench gate/charge gate/charge change change change
capacitor trap trap
Minimum 140F2 6F2 10F2 5F2 20F2 4.8(4)F2b 22F2 4F2c
cell size
Write/erase 0.3 ns/ <10 ns/ 1 ms/ 1 ms/ 10 ns/ 20 ns/ 10 ns/ 5 ns/5 ns
time 0.3 ns <10 ns 10 ms 0.1 ms 10 ns 50 ns 10 ns [48]
Endurance >3 × 1016 >3 × 1016 >105 >105 >3 × 1016 108 1014 >1010 [49]
(cycles)
Application Cache Main Storage Storage Storage Storage Storage Storage/Main
memory memory
a
1D1R (one-diode and one-resistor) unit cells are employed in passive PRAMs and RRAMs, which are based on crossbar-arrays.
b
Passive crossbar-array-based PRAMs satisfy a minimum cell size of 4F2 .
c
Similar to passive PRAMs, passive RRAMs satisfy a minimum cell size of 4F2 .

the remedy by the insertion of internal ‘charge pumps’ in
each cell will decrease yields, increase cost and increase
failure mechanisms [4]. In spite of the wide application
of FLASH memories in commercial products, e.g. digital
cameras, memory sticks and mp3 players, the current FLASH
memory technology has obvious disadvantages: long write and
erase times as well as a limited cyclability of >105 write/erase
cycles compared with DRAM (>3 × 1016 write/read cycles)
(see table 1). Because of these drawbacks, FLASH memories
are not seriously considered as candidates for future secondary
memories.
Similarly, DRAMs, which are omnipresent in today’s
computers, have been meeting all the scalability requirements
since their introduction in the beginning of 1970s, but
a further improvement in the density is a problem. In
2005, DRAM technology entered sub-100 nm technology,
and DRAM capacitor technology is slowly transitioning from
metal–insulator–semiconductor capacitors to metal–insulator–
metal (MIM) capacitors with focus on the design of capacitors
and new high-k dielectrics. The requirements are twofold: (i)
from a material’s point of view, high-k dielectric films with
low leakage current and high breakdown strength are of great
importance, and (ii) from a process’s point of view, the uniform
deposition of high-k dielectric films on three-dimensional (3D)
structures [5–9].
System memory power (DRAM power) and disk power
contribute as much as 40% to the overall power consumption,
and the current trends suggest that this will continue to increase
at a rapid rate. The energy efficiency therefore becomes
a critical aspect. Replacing DRAMs with NVMs may be
the ultimate solution for energy efficiency. However, as an
intermediate stage to save on storage energy, one can connect
a disk to a DRAM via an NVM, or alternatively, extend the
refresh time of the DRAM. This energy efficiency extends the
battery lifetime of mobile systems, and thus the time-period
during which the systems are operational. This is an important
design issue in mobile computer systems.
In short, both DRAM and FLASH memory technologies
will touch the miniaturization limit when the lateral feature
size of DRAMs and FLASH memories shrinks down to 21 nm
(for DRAM technology 2016 and for FLASH technology
2013) [1]. Fortunately, there are emerging memories in
the technology pipeline that may address this concern [1,
10, 11]. Developing a memory technology, which combines
the best features of the current memories with fabrication
that is compatible with the complementary-metal–oxide–
semiconductor (CMOS) process flow and can scale beyond
the present limit of DRAMs and FLASH memories, is a big
challenge [1].
1.3. Emerging memories
There are more than a dozen memories, based on different
concepts, which have been considered as emerging memories.
Examples are ferroelectric RAMs (FRAMs) [12], resistive
RAMs (RRAMs) [13–17], magnetic RAMs (MRAMs) [18],
phase-change RAMs (PRAMs) [19, 20], electrochemical
metallization (ECM) memories or programmable metallization
cell (PMC) memories [14, 21], carbon nano-tube memories
[22], millipede memories [23], molecular memories [24],
nano-crystal floating-gate FLASH memories [25] and DNA
memories [26]. However, among these memories, FRAMs,
RRAMs, MRAMs and PRAMs have been considered as
emerging memories to potentially overcome the limitations
of DRAMs and FLASH memories. The comparison
between the conventional and emerging memories is given in
table 1. PRAMs, MRAMs and RRAMs are resistance-based
memories, whereas FRAMs are based on capacitance. We will
discuss these four memories rather briefly before moving onto
the topic of resistive switching materials.
1.3.1. Ferroelectric memories. When a sufficiently strong
electric field (E > Ec , Ec : coercive field) is applied
to a ferroelectric material, the consequent change in the

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Rep. Prog. Phys. 75 (2012) 076502
ferroelectric polarization is hysteretic in nature. In an ideal
case, a polarization versus electric field loop presents two
distinguishable polarization states. This bi-stability in the
polarization forms the basis of FRAMs [12]. FRAMs,
introduced in the late 1980s a couple of years after FLASH
memories, offer a number of advantages, notably, low-power
consumption, fast write speed and good cyclability (see
table 1) [12].
Currently, Pb(Zr x , Ti1−x )O3 (PZT) and SrBi2 Ta2 O9
(SBT) are used in FRAMs. FRAMs are still considered
as emerging memories, although the expected density in the
gigabit regime has not been achieved so far. It started out
with great promise, a couple of generations behind mainstream
DRAMs and FLASH memories. Current FRAMs have a unit
cell of 1T1C. However, difficulty in scaling up the density
due to the large cell size (12–80F 2 ) compared with DRAMs
and FLASH memories has pinned the density of FRAMs in the
megabit regime and is still a problem to circumvent. Therefore,
a consensus in the community is that high-density FRAM
architecture needs to feature 3D capacitors in order to increase
the capacitor area without increasing the lateral cell size to
obtain the required polarization to retain the signal strength.
Most ferroelectrics have polarization in the range
20–35 µC cm−2 , and thus there is no scope for the
improvement of FRAM density without 3D capacitors. In this
context, multiferroic BiFeO3 (BFO) is of great importance as its
polarization value is more than double that of a standard PZT.
Introducing BFO to 1T1C FRAMs can therefore lead to higher
densities than SBT- and PZT-based FRAMs. Additionally, by
means of 3D capacitor architecture, the density of FRAMs
can be further improved, although this brings about additional
process complexity. 3D ferroelectric nano-capacitors have
been recently demonstrated by Miyake et al and by Fan et al
[27, 28]. However, it is challenging to realize 3D ferroelectric
capacitors, which requires uniform ferroelectric film thickness
on 3D structure with a high aspect ratio.
Also, there are other key integration issues in FRAMs that
still need to be addressed, such as etching technology to impose
less plasma damage on the capacitors, stacking technology for
the preparation of robust ferroelectrics, capping technology
to encapsulate the cell capacitors and vertical conjunction
technology to connect cell capacitors to the plate line [29].
1.3.2. Phase-change memories. Phase-change materials
(PCMs), which are typically higher chalcogenides, exhibit an
ability for reversible phase transition between the amorphous
and crystalline phases with the help of Joule heating. This
phase transition brings about a change in the resistance
as well as the reflectivity. An idea to use PCMs in
memory devices dates back over four decades [30, 31].
However, material quality and power consumption issues have
prevented the commercialization of this technology. The
progress in semiconductor manufacturing technology and the
development of high-quality PCMs during the last few decades
are the main reasons for the recent revival of PCM-based
NVMs, i.e. PRAMs. Optical memories employing PCMs, e.g.
CDs and DVDs, already exist in the memory market. However,
5
D S Jeong et al
these optical memories utilize the change in PCMs’ reflectivity,
rather than resistivity, depending on their phase change.
Currently, PRAMs are promising as emerging memories.
Some electronics companies have already fabricated 512 Mb
PRAMs using the 40 nm technology. PRAMs are expected
to replace NOR-FLASH memories in the memory market at
present. Recent progress in PRAM technology has provided
a clear demonstration of the excellent scaling potential to and
beyond the 16 nm generation [20].
1.3.3. Magnetic memories. MRAMs have been considered
as possible candidates to replace several types of current
memories, such as embedded SRAMs and NOR-FLASH
memories, and, in more advanced generations, perhaps
DRAMs and NAND-FLASH memories. Two main types
of MRAMs have been developed: field-writing MRAMs and
spin-transfer torque MRAMs (STTMRAMs). In a field-
writing MRAM, each memory cell is written by a magnetic
field around the current line. Field-writing MRAMs have been
around for more than 10 years and are currently in production
as stand-alone 16 megabit MRAMs and embedded memories.
The primary issue with field-write MRAMs is their high write
current, which makes scaling difficult.
STTMRAMs which exploit spin-polarized current have
relatively good potential as a next-generation memory type,
combining advantages of SRAMs (high speed), DRAMs
(scalability) and FLASH memories (non-volatility) [32].
However, the OFF/ON ratio is of some concern since it must
increase as the bit line voltage becomes lower. Also of concern
is the energy dissipation during operation.
1.3.4. Resistance memories. Resistance memories
nominally include all types of memories using two or more
distinctive resistance states as the binary numbers ‘0’ and
‘1’. Therefore, PRAMs and MRAMs in principle could be
considered as resistance memories but are relatively much
more clearly understood. When RRAMs were introduced,
the mechanism was not well understood. Pioneers named
this memory type RRAM without specifying the mechanism.
Materials for RRAMs cover all materials exhibiting non-
volatile resistive switching toggled by electric fields, other than
phase-change-type higher chalcogenides.
The resistive switch in each memory cell of a 1T1R-
type RRAM consists of a switching layer and top electrode
(TE) and bottom electrode (BE) sandwiching the switching
layer. This capacitor-like switching cell is characterized by
two distinctive resistance states: a high resistance state (HRS)
and a low resistance state (LRS). By applying either a voltage
or a current to the cell, reversible switching between the HRS
and LRS can be achieved. Once switched, the cell retains the
particular resistance level for a long time.
Reversible resistive switching was observed in various
binary oxides, such as Nb2 O5 , Al2 O3 , SiO2 and TiO2 , more
than four decades ago [33–38]. Later in 1994, Blom et al
observed resistive switching in a different class of materials,
ferroelectrics. They reported a hysteretic current–voltage
(I –V ) behaviour in ferroelectric PbTiO3 (PTO) sandwiched
between Au TE and La0.5 Sr0.5 CoO3 (LSCO) BE [39]. This
Rep. Prog. Phys. 75 (2012) 076502
system has the limitation that the signal level is weak, which is
an obstacle to the application of this system in memory devices
since sense amplifiers and discriminators cannot read the signal
reliably.
Current research on resistive switching started in the
early millennium [15–17, 40–42]. In 2000, Liu et al found
an electric-field-induced resistance-change (EPIR) effect in
perovskite-type Pr x Ca1−x MO3 (PCMO) [16]. In fact, in 1997,
Asamitsu et al demonstrated resistive switching in PCMO,
toggled by not only a magnetic field but also an electric
field [43]. In 2000, resistive switching was also found in
another perovskite-type oxide, Cr-doped SrZrO3 (SZO), and
the application of this material in NVMs was demonstrated
[15]. These findings triggered enormous interest in resistive
switching in oxides for application in RRAMs, which had been
out of the minds of researchers for more than three decades.
This attention inspired much research on resistive switching
in various oxides, not only perovskite-type oxides but also
simple binary transition metal oxides (TMOs) and wide band
gap high-k dielectric oxides.
An enormous number of papers on resistive switching
deal with a large number of materials with different
functionalities, e.g. dielectric, paraelectric, ferroelectric,
ferromagnetic and semiconducting materials. Materials with
contrasting properties, i.e. different functionalities, show
universal resistive switching. This sort of universality makes
understanding of the phenomena complicated. There have
been more than 1000 publications in the last ten years on
resistive switching according to the Web of Science7 . From
these publications it can be seen that the physics of resistive
switching has not been fully understood. Moreover, there are
many publications addressing different switching behaviours
even in the same systems, which make the understanding even
more difficult.
Resistance memories such as PRAMs and RRAMs are
inherently more free from scaling problems than capacitance-
based memories such as DRAMs and FRAMs. Crossbar-
array-based passive RRAMs appear to achieve a design rule of
4F 2 due to the lack of MOSFET cell selectors. Of course, some
critical issues, for instance, the prevention of sneak current
for the worst-case pattern, should first be solved. When the
operation speed of RRAMs catches up, DRAMs could be
replaced, which would allow systems to power on and off
without rebooting. Moreover, RRAMs could be substitutes
for hard disks once they achieve comparable life spans.
There are a number of review papers on resistive switching
[13, 14, 38, 44–47]. However, most of them only partially deal
with switching materials. In the present review, we address
almost all switching materials and the important basics of
resistive switching.
2. Basics of resistive switching
Several insulating materials sandwiched between two
electrodes (MIM) show hysteretic I –V characteristics. The
origin of the I –V hysteresis appears to be twofold: time-
dependent ac current and hysteretic dc current. The former
7 wok.mimas.ac.uk
6
D S Jeong et al
case can be seen in highly resistive dielectrics in which the dc
current flow is much lower than the ac current. Hysteretic
I –V behaviour with ac current relies on a voltage sweep
rate, i.e. with decreasing sweep rate, the hysteresis shrinks.
If the delay time of each step in a stair-case voltage sweep
is longer than the capacitance charging/discharging time, the
hysteresis disappears. Therefore, this I –V hysteresis should
be distinguished from dc current versus voltage hysteresis.
Dietz and Waser have suggested a method to extract a dc current
contribution out of mixed dc and ac current contributions in
high-k dielectrics [50].
However, some MIM cells show ‘dc current’ versus
voltage hysteresis with characteristic threshold voltages, and
some distinctive resistance states in the sub-threshold voltage
region. Namely, they are non-volatile resistive switches. The
available number of stable resistance states in the sub-threshold
region is at least two, which is enough to write binary values.
This hysteretic behaviour makes the switch stay in the HRS or
LRS unless the applied voltage exceeds the threshold voltages.
Additionally, the switch locks onto these two stable states even
if a voltage is reduced to zero, making it remember the last
action. More importantly, the switching between these HRS
and LRS can be programmed by the application of appropriate
voltages many times. Hence, the term ‘resistive switching’
thereby forms the basis of the new rewritable non-volatile
RRAMs.
A conducting filament (CF) that acts as a circuit
breaker/switch between two electrodes is believed to be
responsible for most resistive switching phenomena. The
breaking and forming of a CF occurs over a nanometre-scale
region within very short times at the nanosecond scale. In this
chapter, we briefly discuss the basics of resistive switching
such as types of resistive switching behaviours and switching
measurement methods.
2.1. Types of resistive switching
Currently, the scientific community on resistive switching has
agreed on the presence of unipolar and bipolar switching
in various switching materials. Resistive switching can
be classified into unipolar and bipolar switching by the
number of degrees of freedom for an operational input.
Unipolar switching involves only one degree of freedom:
the amplitude of the applied input (voltage/current), whereas
bipolar switching involves two: the amplitude and the polarity.
Unipolar and bipolar switching behaviours are given by
functions of a scalar and a vector variable, respectively.
Since unipolar switching does not rely on the polarity of the
applied input, I –V loci showing set (HRS→HRS) and reset
(LRS→HRS) switching can be plotted in both the first and
third quadrants of an I –V graph.
As illustrated in figure 2, we define I –V loci of set and
reset switching for voltage application as fset (V ) and freset (V )
in the first quadrant of an I –V plane. Unipolar switching
can present any combination of set and reset switching
curves in a set of ((fset (V ) or −fset (−V )) and (freset (V )
or −freset (−V ))), i.e. four combinations are possible. Note
that some combinations, (fset (V ) and −freset (−V )) and
Rep. Prog. Phys. 75 (2012) 076502
Figure 2. Possible combinations of set and reset I –V curves. For
unipolar switching, all four combinations are possibly observed,
whereas for bipolar switching only (b) and (c) curves are possible.
In bipolar switching, (b) and (c) combinations are called ‘counter
eightwise’ and ‘eightwise’ switching curves, respectively [51, 52].
(−fset (−V ) and freset (V )), for unipolar switching typically
describe bipolar switching as well. As a matter of fact,
observations of these set and reset loci do not necessarily imply
bipolar switching, so that one needs special caution when the
switching type of investigated switching systems is judged by
their set and reset I –V curves.
In bipolar switching, both amplitude and polarity of the
applied input must satisfy proper conditions for the operation.
Possible combinations of I –V curves for bipolar set and reset
switching are (fset (V ) and −freset (−V )) and (−fset (−V ) and
freset (V )) shown in figures 2(b) and (c), respectively. They are
sometimes referred to as ‘counter eightwise’ and ‘eightwise’
bipolar switching curves, respectively [51, 52]. In order to
identify bipolar switching one should make sure that the other
combinations of set and reset loci do not appear. In old
terminology, bipolar switching was referred to as ‘polarized
memory switching’. Many papers published in the 1970s used
this terminology.
One can define four different resistance states of a
switching cell: as-fabricated state, as-electroformed state, HRS
and LRS. As most switching materials are initially insulators,
the as-fabricated switching cell is most resistive among the
four states. As an initialization step for resistive switching
measurement, one needs an electroforming process that is
typically conducted by applying a high voltage/current to the
as-fabricated switching cell. The electroforming process leads
to a large decrease in the resistance. In general, the as-
electroformed state is comparable to the LRS. The resistance in
the HRS is most likely lower than the as-fabricated state [53]. It
seems that the reset switching cannot recover the as-fabricated
resistance state.
7
D S Jeong et al
Figure 3. Schematics of (a) traditional electroforming and
(b) electroforming in resistive switching.
2.2. Resistive switching measurements
For switching measurements, one can use various input
bias sources such as voltage/current sweeps and constant
voltage/current pulses. Voltage/current sweeps are frequently
used for the simple and quick identification of switching
behaviour, whereas the application of voltage/current pulses is
useful for quantitative investigation on switching kinetics. For
successful switching measurements, one should use caution in
choosing an input bias source, whether a current or a voltage,
and a compliance current if a voltage source is used.
In unipolar switching, the HRS-to-LRS ratio appears to be
several orders of magnitude, although it has large distribution
depending on the switching and electrode materials and
measurement conditions. Therefore, the resistance-state-
dependent variation of the power dissipation is very high. Both
voltage and current sources are available for set switching. For
voltage source applications, a compliance current needs to be
programmed for the set switching to protect the switching cell
from dielectric breakdown.
Unlike set switching, a current source may not be available
for reset switching. When reset switching occurs under a
current sweep, a large increase in the power dissipation will
take place resulting from a large increase in the resistance.
This very abrupt increase in the power dissipation may lead
to dielectric breakdown rather than reset switching. None of
the literature has dealt with current-driven reset switching in
unipolar switching. For voltage source applications, a large
decrease in the power dissipation during reset switching occurs
so that dielectric breakdown does not occur. However, both
voltage and current can be successfully used as an input bias
source for bipolar switching measurements [53].
3. Electroforming
Traditionally, ‘electroforming’ denotes an electrochemical
process for metallic structure formation. The working prin-
ciple of electroforming is identical to that of ‘electroplating’,
which exploits reduction and oxidation (redox) reactions of
metallic elements to be plated on the surface of an object at
the cathode. Electroforming differs from electroplating in the
sense that the electroformed metal structure is free-standing
because the mandrel is removed after the electroforming
(figure 3).
In resistive switching, a pretreatment process is necessary
in order to activate resistive switching in a switching
Rep. Prog. Phys. 75 (2012) 076502
material. This process is called either ‘electroforming’ or
simply ‘forming’. Electroforming in resistive switching is
believed to lead to the creation of CFs in the insulating
matrix. This electroforming may have some similar aspects
to the traditional meaning of electroforming. For instance,
both electroforming processes create electrically conductive
objects. Also both processes involve electron transfer via
ions, i.e. redox reactions. Redox reactions in electroforming
for resistive switching will be discussed later. What
most fundamentally distinguishes electroforming in resistive
switching from the traditional one is that the reversibility
between the formation and rupture is critical in electroforming
for resistive switching, whereas traditional electroforming only
concerns the formation of metallic structure.
In order to electroform a pristine resistive switching cell,
one should impose high electrical stress on the cell. This can
be simply done by applying either a voltage or a current to
the cell. The high electrical stress leads to the formation
of CFs and the consequent decrease in the cell’s resistance
by several orders of magnitude. Let us suppose that we
perform electroforming on a pristine switching cell using a
voltage source, e.g. a constant voltage and a voltage sweep.
A large decrease in the cell’s resistance at a certain voltage
(electroforming voltage) leads to a large increase in the power
dissipation, and the power dissipation easily goes out of
control. This may consequently result in the destruction of the
cell (dielectric breakdown). Fortunately, most commercialized
voltage sources provide a current compliance function that
is able to control the maximum current (compliance current)
allowed through the cell. Therefore, one can avoid dielectric
breakdown by programming a proper compliance current.
Dielectric breakdown differs from electroforming in the sense
that it leads to a permanent resistance decrease so that
switching back to the HRS is impossible.
In spite of such a compliance current function, a critical
problem of the current overshoot occurring when the current
reaches the compliance current cannot be avoided. This
problem leads to an uncontrollable effect on the subsequent
resistive switching behaviour [54]. However, if a current
rather than a voltage source is employed in electroforming,
programming a compliance current is unnecessary so that the
overshoot issue can be avoided. In fact, a current-driven
electroforming process in TiO2 has been found to result in
a more reliable transition into the bipolar switching mode
without unexpected transitions into the dielectric breakdown
or unipolar switching states [55].
Electroforming triggers localized current conduction by
introducing CFs, which was first suggested by Dearnaley in
1967 [56]. Many imperfections in the switching cell, e.g.
interfacial roughness between the electrode and switching
materials, voids, and compositional inhomogeneity, may lead
to the non-uniform distribution of the internal electric field,
which may play a role in the formation of CFs [38]. The
growth of CFs may follow the winner-take-all procedure [57]
as do neurons and synapses in animal brains. A winning CF
obtains more strength during the growth, which arises from
a higher electric field in the vicinity of the CF and (or) the
consequent high local temperature. It has been found that the
8
D S Jeong et al
Figure 4. Current-sweep-driven electroforming for TiO2
sandwiched between Pt BE and Pt/Ti bilayer TE. The lower Ti layer
in the TE is in contact with the TiO2 layer. The junctions have five
different pad sizes, 100 × 100, 200 × 200, 300 × 300, 400 × 400
and 500 × 500 nm2 . Reproduced with permission from [55].
Copyright 2010, American Institute of Physics.
resistance of electroformed cells does not scale with the pad
size. This implies a non-uniform distribution of the winning
CFs over the whole pad area.
The evolution of non-scaling resistance/conductance with
regard to electroforming procedures can be directly monitored
by applying a current sweep and simultaneously measuring
a voltage across each switching cell of different pad sizes
(see figure 4). Pt/Ti/TiO2 /Pt cross-point junctions, when
initially in the low current region, exhibit well-scaling pad-
size dependence, and begin to evolve non-scaling pad-size
dependence as the applied current is increased. Then, the
current at the electroforming moment (Ief ) is found to be
proportional to the electrode line width rather than the pad
size, perhaps implying enhanced current conduction along the
perimeter of the cross-point junctions at Ief [55]. This may be
attributed to the enhanced electric field at the perimeter, i.e. the
fringing effect [55]. Right after the sudden decrease in voltage,
the electroformed state is finally achieved for each junction,
and then the resistance/conductance scaling with neither the
pad size nor the line width is found, as shown in figure 4.
For a better understanding of electroforming kinetics, real-
time monitoring of the current responding to a voltage applied
to a switching cell would be helpful. Applying a constant
voltage with a fast rise-time square pulse, rather than a voltage
sweep, would make the analysis simpler. This is also true for
the current-application and voltage-measurement cases.
However, electroforming by this method is likely to lead
to largely scattered resistance states as shown in TiO2 with
symmetric Pt TE and BE [58] and also asymmetric Pt/Ti TE and
Pt BE [55]. Regarding proper conditions for electroforming
into bipolar switching in TiO2 , Nauenheim et al have drawn
the conclusion that the application of a negative current sweep
to the TE at a rate of several hundred nA/s results in the most
reliable bipolar switching [55].
Let us take a close look at some experimental evidence
from which we can qualitatively deduce a mechanism for
electroforming. Note that a mechanism for electroforming has
not been fully understood so far, so that this section will include
some speculations. We will focus on non-stoichiometric
Rep. Prog. Phys. 75 (2012) 076502
Table 2. Major electronic carrier types of several TMOs of various valence states. Blanks in the table mean either that the corresponding
TMOs are metallic or that they do not exist as stable phases.
Ti–O V–O Cr–O
+1 (M2 O)
+2 (MO)
+2.66 (M3 O4 )
+3 (M2 O3 ) n or p [61, 62]
+4 (MO2 ) n [62] n [63]
+5 (M2 O5 ) n [62]
Cu–O Nb–O Ta–O
+1 (M2 O) p [62]
+2 (MO) n or p [62]
+2.66 (M3 O4 )
+3 (M2 O3 )
+4 (MO2 ) n [64]
+5 (M2 O5 ) n [65] n or p [66]
+6 (MO3 )
binary TMOs, especially TiO2 and NiO, which are well-known
n-type and p-type semiconductors, respectively [59].
A large number of binary TMOs are resistance-switchable.
Since transition metal ions can vary their valence states, a
number of point defects with a certain limitation can be
included in a TMO matrix without phase transition. This
leads to non-stoichiometry, which can be described as MOx+δ ,
where ‘M’ and ‘O’ denote transition metal ion and oxygen ion,
respectively. Non-stoichiometric TMOs are classified as hypo-
and hyper-stoichiometric oxides relying on the sign of the
deviation δ, the former and latter take the negative and positive
deviations, respectively. The introduction of charged point
defects in a TMO matrix leads to a change in the electronic
carrier concentration so that this is effectively identical to an
extrinsic doping effect (self-doping). The major electronic
carrier types of hypo- and hyper-stoichiometric TMOs are
electrons and holes, respectively. The major electronic carrier
type of several TMOs of different valence states is summarized
in table 2.
Based on experimental observations, we can summarize
remarkable phenomena occurring during electroforming: (i)
electrolysis (anodic) reactions and ion migration, (ii) resistance
change, and (iii) phase transition and Joule heat. They will
be separately discussed in detail in sections 3.2–3.4. Before
we go through recent observations in electroforming, we
will give a brief overview on several early mechanisms for
electroforming, which were mostly introduced in the 1960s
and 1970s.
3.1. Early mechanisms for electroforming
Some mechanisms for electroforming, i.e. S-shaped I –V
behaviour, were suggested in the 1960s and 1970s by pioneers
in the field. An overview on these mechanisms is nicely
presented in the review paper by Dearnaley et al [38]. Hickmott
saw electroforming from a purely electronic point of view
[68, 69]. In this model, the ionization of immobile impurities
at the electroforming leads to the evolution of an impurity
energy band in the forbidden gap so that electrons in the
cathode can inject into the impurity energy band without a
thermionic emission process. Regarding the origin of the
9
D S Jeong et al
Mn–O Fe–O Co–O Ni–O
p [60] p [60] p [60] p [60]
p [59]
n [62]
n [62]
W–O
n [67]
impurity energy band, the model by Simmons and Verderber
differs from Hickmott’s model because they assumed metal
ions injected from the anode to result in the impurity band [70].
Although the authors did not explicitly mention a mechanism
for metal ion injection, in context it can be estimated that the
injection occurs in an electrical manner through electrostatic
forces on the ionized metal atoms. Basically, these two models
presume the electronic transport through the junction to be
band conduction by delocalized electrons.
According to Barriac et al, metal ion injection from the
anode into the insulating layer was estimated to be a result
of the local fusion of the anode and insulator, induced by
the large power dissipation during electroforming [71]. This
model differs from the model by Simmons and Verderber in
the mechanism for metal ion injection. Electric current in
the model by Barriac et al is attributed to ionic as well as
electronic current by quantum mechanical tunnelling through
the insulating barrier.
Greene et al [72] approached an electroforming mecha-
nism from a different point of view from the aforementioned
mechanisms. In their model, the electrochemical reactions in
insulator ‘MX’, the oxidation of anion ‘X − ’ (X − → X + e− )
at the anode and the reduction of monovalent cation ‘M + ’
(M + + e− → M) at the cathode were assumed to take place,
and anion vacancies are injected from the ‘cathode’. That is,
this model presumes phase separation in the insulator and gas
evolution at the anode. However, it is hard to understand that
anion vacancies are injected from the ‘cathode’ because in
general anion vacancies are supposed to be introduced at the
anode as a result of an anodic reaction, X − → X + e− , that
×
is, XX → VX· + e
in the Kröger–Vink notation [73]. Greene
et al regarded electron hopping along ordered –M–vacancy–
M– chains as the conduction mechanism in the electroformed
state.
Dearnaley et al emphasized that electroforming leads to
CFs, i.e. localized conduction [74]. Earlier, Dearnaley had
pointed out that the CFs begin to grow at several points at the
insulator/anode interface, where the local electric fields are
high [56]. The growth direction of the CFs, which Dearnaley
suggested, is inconsistent with the models based on virtual
cathode migration due to drift–diffusion of point defects.
Rep. Prog. Phys. 75 (2012) 076502
Figure 5. Scanning electron microscope (SEM) images of Pt/TiO2 /Pt switching cells electroformed by applying (a) a positive voltage and
(b) a negative voltage to the 10 nm thick TE, respectively. The inset is a cross-sectional SEM image along the dashed line in figure (b).
Reproduced with permission from [53]. Copyright 2009, Forschungszentrum Jülich.
Details of this model are discussed in section 3.2. Electron
hopping along one-dimensional chains was estimated to be the
dominant conduction mechanism in the electroformed state.
Dearnaley et al also assumed an anodic reaction involving
oxygen gas evolution to occur at the anode.
The mechanisms by Greene et al and Dearnaley et al
regard switching cells as open systems exchanging oxygen gas
with atmosphere (oxygen reservoir). Greene et al introduced
a model of the incorporation of oxygen gas in air into
the insulator as a result of the cathodic reaction, 1/2O2 +
2e− → O2− [72]. In terms of Greene’s and Dearnaley’s
hypotheses, the electrode dependence of electroforming can
also be understood. These models consider possible oxidation
reactions at the insulator/anode interface between the oxygen-
reactive electrode and evolved oxygen gas, and point out that
these oxidation reactions lead to second oxide phases hindering
the electroforming [72, 74].
Over more than two decades, Chudnovskii et al
conjectured that electroforming in some anodic binary TMOs,
such as TiO2 , V2 O5 , Fe2 O3 and Nb2 O5 , leads to phase
transition from the highest oxides (most resistive) to lower
oxides (less resistive) [75]. Their prediction was based on
simple free energy calculations of lower oxide formation
reactions, for instance, Nb + 2Nb2 O5 → 5NbO2 . The
calculated energies were found to be negative, i.e. spontaneous,
and the Joule heat generated during the electroforming was
thought to accelerate these spontaneous reactions [75]. Note
that this calculation is only valid for a TMO (MOx ) film on an
‘M’ electrode.
3.2. Electrolysis (anodic) reactions and ion or ionic defect
migration
As observed by Greene et al [72] and Dearnaley et al [74], oxy-
gen gas formation and subsequent structural deformation have
been frequently observed in several switching oxides such as
SrTiO3 (STO) [76], Fe-doped STO [51] and TiO2 [53, 58, 77].
The gas evolution most likely results from the electrolysis (ano-
dic) reaction, 2O2− → 4e− + O2(g) , implying that the number
of anions in the oxides is not conserved and the electroforming
is affected by the partial pressure of atmospheric oxygen gas
because the reverse reaction also occurs.
10
D S Jeong et al
In a Pt/TiO2 /Pt cell, it has been identified that oxygen
gas is evolved at the anode by measuring the dependence of
morphological changes on the polarity of the electroforming
voltage (see figures 5(a) and (b)). When TE was used
as the anode (figure 5(a)), the TE locally disappeared,
which may result from the eruption of oxygen gas through
the TE. The formation of doughnut-shaped explosive spots
during electroforming and set switching was already found
in Au/ZrO2 /Zr unipolar switching cells more than 40 years
ago (1970) [78]. When BE was used as the anode
(figure 5(b)), the formation of bubbles was found underneath
the switching cell. Similar observations have been reported
in ferroelectric films: the local phase decomposition due to
repeated ferroelectric switching and numerous bubbles in 1010 -
cycle-fatigued electrodes after re-annealing in oxygen [79].
Anodic reactions have also been found in the
electroforming of Cr-doped SZO [80]. X-ray absorption near-
edge spectroscopy (XANES) at the Cr absorption K-edge, in
fact, revealed that the electroforming leads to the oxidation of
doped Cr ions underneath the anode and no valence change of
those underneath the cathode [81]. However, XANES analysis
on the area between the anode and cathode showed that oxygen
vacancies rather than Cr ions were responsible for the CF
formation [80]. More oxygen vacancies were found in the
vicinity of the anode than near the cathode, and hence the anode
is thought to be an oxygen vacancy source resulting from the
anodic reaction, 2O2− → O2(g) + 4e− , that is, O× ··

O → VO + 2e
in the Kröger–Vink notation [73].
If a noble metal such as Pt or Au is used as the anode
of a switching cell, the oxygen gas can be incorporated into
the anode, as a result of the anodic reaction, which then
forms chemisorption bonding with the anode metal. Noble
metals form very strong and dense chemisorption bonding with
oxygen atoms at their surface within a few monolayers instead
of metal-oxide phases [82]. Pt is especially regarded as a
catalyst for oxygen gas decomposition [82]. The incorporation
of oxygen into the Pt anode of a ferroelectric junction was first
identified by Jung et al [83]. Subsequently, oxygen in the Pt
anode of an electroformed Pt/TiO2 /Pt switching cell has been
identified by time-of-flight secondary ion mass spectrometry
(TOF-SIMS) analysis by Jeong et al (see figure 6) [58]. The
Rep. Prog. Phys. 75 (2012) 076502 D S Jeong et al

Figure 6. (a) Oxygen ion signal of TOF-SIMS analysis, integrated over depth on a 100 × 100 µm2 Pt TE. This switching cell was
electroformed by applying a positive voltage to the TE. The depth profiles of each element at a dark point (A) and a bright point (B) are
plotted in (b) and (c), respectively. The depth profile of oxygen in the TE at B shows a higher concentration of oxygen than A, which is
almost identical to that in the pristine. Reprinted with permission from [58]. Copyright 2008, American Institute of Physics.

distribution of oxygen in the TE over the TE area was found to
be non-uniform as shown in figure 6(a). However, if the anode
metal is oxygen-reactive, the evolved oxygen gas perhaps
reacts with the anode metal, introducing a second metal-oxide
phase(s) at the interface between the anode and switching oxide
layers. For instance, an Al anode would form a very thin but
highly insulating oxide layer at the interface, and thus this layer
probably hinders the transition into the electroformed state as
expected by Greene et al [72] and Dearnaley et al [74].
Many hypo- and hyper-stoichiometric TMOs, shown in
table 2, are resistance-switchable. Dealing with detailed
electroforming mechanisms of all the switching TMOs is
beyond the scope of this review paper. TiO2 and NiO
are examples of hypo- and hyper-stoichiometric TMOs,
respectively [59], and their electroforming mechanisms will
be discussed in detail. Before we begin to go through
the mechanisms, it will be helpful to discuss the basic
defect chemistry of non-stoichiometric binary TMOs. Hypo-
stoichiometry (MOx−δ , δ > 0) results from the formation of (i)
oxygen vacancies or (ii) cation interstitials [84]. For simplicity,
let us consider divalent transition metal ion, M 2+ , i.e. x = 1 in
MOx−δ . The formation reactions for (i) and (ii) are expressed
in the Kröger–Vink notation [73] as
1 O2(g) → OO× + VM + 2h· ,
O×
O → VO··

+ 2e + O2(g) (1)
2
and
×
1
MM + O× ··
O → Mi + 2e + O2(g) , (2)
2 metal monoxides with divalent transition metal ion, e.g. NiO,
respectively. These defects are inherently present in hypo-
stoichiometric MOx−δ , and additional ones can be introduced
by thermodynamic and/or electrochemical reduction. As
shown in equations (1) and (2), both defects introduce two
delocalized (free) electrons and thus serve as donors. The
population of free electrons therefore increases so that MOx−δ
is an n-type semiconductor. The defect structure of non-
stoichiometric TiO2 was controversial, whether the hypo-
stoichiometry arises from equation (1) [85–88] or equation (2)
[89–91]. However, as Marucco et al have demonstrated,
the dominant defect type in TiO2 is believed to depend on
temperature; oxygen vacancy and Ti interstitial are low-
and high-temperature-stable defect types, respectively [87].
Therefore, the major defect type in TiO2 at room temperature,
concerned with electroforming, is most likely oxygen vacancy
rather than Ti interstitial.
On the other hand, hyper-stoichiometry (MOx+δ , δ > 0)
arises from the formation of (iii) oxygen interstitials or (iv)
cation vacancies [84]. Again let us regard the transition metal
ion to be divalent. The formation reactions for (iii) and (iv) are
written in the Kröger–Vink notation [73] as
1
O2(g) → Oi·· + 2h· (3)
2
and
1


(4)
2
respectively. These defects are the results of thermodynamic
and/or electrochemical oxidation. They serve as acceptors
so that MOx+δ is a p-type semiconductor. Several transition
CoO, MnO and FeO, are known to be cation-vacancy-dominant
hyper-stoichiometric TMOs [60].

11
Rep. Prog. Phys. 75 (2012) 076502 D S Jeong et al

In electroforming, an electrolysis reaction occurs by

equation (1) or (2) at the anode, leading to the reduction of the
TMO [53, 58, 76]. This means that the anode serves as a defect
source. A switching cell under electroforming conditions is
thought to consist of a defect source (anode), a sink (if ever
exists) and a spacer, which is resistive for ion/defect migration,
separating the source and sink [53, 58, 76]. In TiO2 , oxygen
vacancies are introduced by equation (1) at the source (anode).
This point defect type is the same as the inherent major defect
type, and hence the inherent and additional oxygen vacancies
move towards the cathode through the spacer. Unless the
cathode contains a large number of oxygen ions that are able
to annihilate the oxygen vacancies, the cathode cannot serve
as a sink. The oxygen vacancies are therefore piled up at
the cathode, and an oxygen-deficient phase grows from the
cathode to the anode. This implies that the migration of the
virtual cathode towards to the anode occurs.
In NiO, it is conjectured that oxygen vacancies rather
Figure 7. Bright field TEM image of a NiO single crystal that was
than nickel interstitials are formed when reduced [92, 93]. reduced by means of ion bombardment at room temperature. The
Hence, the anodic reaction during electroforming may lead black spots and squares are Ni metallic islands. Adapted from [96].
to oxygen vacancies rather than nickel interstitials. Rodriguez Copyright 1982, Elsevier.
et al have experimentally and theoretically identified the role of
oxygen vacancies in the thermal reduction of NiO [92]. NiO
is thought to have an inherent defect type of nickel vacancy
rather than oxygen interstitial [94, 95], so that the two different
types of defects, oxygen and nickel vacancy, coexist in the
electroforming.
Oxygen and nickel vacancies migrate towards the cathode
and the anode, respectively, under an electroforming voltage.
In the initial phase of electroforming, NiO does not have an
obvious nickel vacancy source because the cathode blocks
nickel ions unless the nickel ions/atoms have high solubility
in the cathode. Without a nickel vacancy source, the
concentration of nickel vacancies near the cathode soon
decreases as they migrate towards the anode. Simultaneously,
oxygen vacancies from the anode are piled up at the
cathode as discussed earlier. For higher concentrations of
accumulated oxygen vacancies at the cathode, there are higher
amounts of single-phase instability of NiO at the cathode. Figure 8. Time-resolved x-ray diffraction of a NiO powder
Thermodynamics does not allow oxygen-deficient NiO. As a annealed in reduction ambient (5% H2 /95% He) at elevated
result, NiO near the cathode may undergo phase separation temperatures at a constant rate of 20 ◦ C min−1 . Reprinted with
permission from [92]. Copyright 2001, American Chemical Society.
into Ni and NiO. In the Kröger–Vink notation [73], this phase-
separation reaction is sequentially expressed as The phase separation of a reduced NiO single crystalline



Ni× ·
→ VNi (NiO) + 2h (NiO) + Ni(s) (Ni) (5) phase into Ni and NiO phases has already been found by
Ni (NiO)
means of a transmission electron microscope (TEM) [96].
and In this study, NiO was reduced by ion bombardment at


room temperature, which removed oxygen ions at the surface.
VNi (NiO) → 2h· (NiO)+VO·· (NiO) + 2e
(NiO) → null(Ni),
The phase separation led to Ni islands at the nanoscale,
(6) which is shown in figure 7. Moreover, thermally reduced
where NiO and Ni in parentheses denote where the given NiO single crystals and powders that were annealed in an
defects are present. By these reactions, the metallic Ni phase He–H2 atmosphere at temperatures in the range 250–350 ◦ C
grows from the cathode to the anode. When the Ni phase underwent NiO-to-Ni transition in which oxygen vacancies
touches the anode, the electroformed state is finally achieved. played a key role [92]. The evolution of a metallic Ni phase
The Ni phase cannot grow from the anode because the with respect to annealing temperatures that were increasing at
reduction of Ni ions cannot take place at the anode. Moreover, a rate of 20 ◦ C min−1 was measured by time-resolved x-ray
equation (5) points out that the phase boundary between Ni diffraction, as shown in figure 8.
and NiO works as a source of nickel vacancies (inherent major Procedures of Ni filament growth during electroforming
defects), which did not exist before the phase separation. are illustrated in figure 9(a). For comparison with a

12
Rep. Prog. Phys. 75 (2012) 076502
Figure 9. Schematic of CF growth in (a) hyper-stoichiometric NiO and (b) hypo-stoichiometric TiO2 . The red arrows indicate the migration
direction of oxygen vacancies and the navy that of Ni vacancies.
hypo-stoichiometric TMO, CF growth procedures in hypo-
stoichiometric TiO2 are also illustrated in figure 9(b). These
CFs can be ruptured and reformed during the subsequent
switching operation. For TiO2 and NiO, the location of the
active regions where the CF rupture and reformation occur
will be discussed in section 4.4.2.
From the electroforming mechanisms of these prototypi-
cal hypo- and hyper-stoichiometric TMOs, we can draw gen-
eral conclusions about the features of electroforming behaviour
of TMOs, which have CFs consisting of lower oxide phases or
even metallic phases, as follows: (i) the transition into a lower
valence state is a result of the electrochemical reduction of the
highest (pristine) valence state, and (ii) the reduction reaction
most likely occurs at the cathode, and thus CFs grow from the
cathode to the anode.
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D S Jeong et al
3.3. Resistance change during electroforming
In hypo-stoichiometric TiO2 , the charge neutrality condition is
fulfilled by reduced Ti ions following the reduction reaction,
Ti4+ + ne− → Ti(4−n)+ . This reaction increases the population
of free electrons in the conduction band, which consists
of 3d orbitals of the Ti ions. The oxygen-deficient phase
growing from the cathode during the electroforming contains
a large number of reduced Ti(4−n)+ ions, and thus the
phase’s conductivity is much higher than the stoichiometric
phase. Moreover, the role of the cathode/TiO2 interface in
electron blocking may become less obvious with increasing
concentration of oxygen vacancies. Details of this relationship
will be dealt with in section 4.4.1. It can be estimated that the
migration of the virtual cathode of the TiO2 switching cell leads
Rep. Prog. Phys. 75 (2012) 076502
Figure 10. High-resolution TEM image of (a) a cone-shaped CF of a Magnéli phase (Ti4 O7 ) in a TiO2 matrix [98] and an hourglass-shaped
CF of two Magnéli phases (Ti4 O7 and Ti5 O9 ) [99]. Reprinted with permission from [98, 99]. Copyright 2010, Nature Publishing group, and
2011, American Institute of Physics, respectively.
to the shrinkage of the effective length of the TiO2 resistor,
implying a decrease in the resistance.
For NiO, the phase boundary between Ni and NiO serves
as the virtual cathode, and also moves towards the anode. The
effective length of the NiO resistor also decreases as the virtual
cathode moves. One can therefore draw the conclusion that the
resistance degradation during electroforming arises from the
migration of the virtual cathode towards the anode regardless
of the non-stoichiometry types, hypo- or hyper-stoichiometry.
When the virtual cathode reaches the anode, abrupt degradation
of the resistance occurs, as shown in figure 4. Then, the
electroformed state is eventually achieved.
Resistance degradation in ferroelectric perovskite-type
complex TMOs, e.g. PZT, has been found to exhibit
complicated phenomena including phase separation into
several phases. For instance, in PZT, ‘nano-shorts’, meaning
the formation of CFs at the nanoscale, is thought to be
responsible for resistance degradation [97].
3.4. Phase transition
After the theoretical expectation of electroforming-induced
phase separation in some binary TMOs by Chudnovskii et al,
CFs in TiO2 were directly observed by Kwon et al by means of
TEM in 2010 [98]. They found CFs consisting of the Magnéli
phase (Tin O2n−1 , n = 4), implying that phase transition is also
involved in electroforming as well as resistive switching. Kim
et al later observed another Magnéli phase (Tin O2n−1 , n = 5)
in CFs [99]. Figures 10(a) and (b) show the cross-sectional
TEM images of a cone-shaped CF (Ti4 O7 ) and an hourglass-
shaped CF (Ti4 O7 and Ti5 O9 ), respectively. Strachan et al
also found a phase transition, from TiO2 to Ti4 O7 , in TiO2 by
a scanning transmission x-ray microscope (STXM) as well as
a TEM [101]. STXM analysis identified multivalent Ti ions,
Ti3+ and Ti4+ , in CFs, which does not necessarily imply phase
transition. However, TEM analysis with STXM measurement
could identify the phase transition.
Phase transition in Pt/CuO/Pt unipolar switching cells
has been reported by Yajima et al [100]. They showed the
electroforming-induced formation of an oxygen-deficient CF
connecting the anode and cathode by SIMS analysis (see
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D S Jeong et al
figure 11). They also demonstrated that the oxygen-deficient
CF consists of two different Cu–O phases, CuO and Cu2 O,
using Raman spectroscopy, which is shown in figure 11(c).
Electroforming is therefore generally understood in terms
of nano-short (nano-filamentary conductive path of a different
phase(s) from the host pristine phase). Nano-short generally
involves a dendrite-shaped ‘moving (virtual) cathode’, which
was first studied in detail by Plumlee at Sandia in 1967 [102].
Nano-shorts in ferroelectric PZT are thought to be caused by
the phase transition of PZT. Micro-Raman spectroscopy with
a spatial resolution of 1 × 1 µm2 on fatigued regions of a PZT
film identified the chemical decomposition of PZT into litharge
and massicot forms of PbO, together with the production
of rutile TiO2 [79]. This was the first direct verification
of phase transition in nano-shorts. Fatigued ferroelectrics
share several aspects with electroforming-induced phenomena,
such as the formation of CFs (nano-shorts), phase transition
or phase separation, and evolution of gas bubbles [79, 97].
Annealing fatigued Pt TEs on a PZT film results in gas
bubbles, which are probably oxygen gas from volatile Pb or
PbO [79]. Although direct correlation between ferroelectric
fatigue and electroforming has not yet been clarified, there
are phenomenological similarities between the two seemingly
unrelated processes.
For the phase transition of TMOs, a certain amount
of thermal energy is necessary. The Joule heat generated
during electroforming is most likely responsible for this
thermal energy. Electroforming results in morphological
changes (demolition) (see figure 5). The volcano-like shapes
indicate that melting and gas (most likely oxygen) eruption
simultaneously occurred during electroforming. The changes
imply that the cell became very ‘hot’ during the electroforming
and the cell’s temperature was high enough to melt the Pt
electrode. The melting temperature of Pt is approximately
2041 K.
3.5. Electroforming into unipolar or bipolar switching
For both unipolar and bipolar switching, almost the same
electroforming process is used. However, what activates only
one of the two different types can be found in switching
Rep. Prog. Phys. 75 (2012) 076502
Figure 11. Oxygen, (a) 16 O and (b) 18 O, distribution in an electroformed lateral Pt/CuO/Pt device, measured by two-dimensional SIMS
analysis. An oxygen-deficient CF connecting the anode and cathode can be seen in the figures. (c) Raman spectra of the CF and
non-filamentary area, which identify the presence of the cuprous oxide phase (Cu2 O) in the CF. Reprinted with permission from [100].
Copyright 2010, The Japan Society of Applied Physics.
systems in which both switching types coexist, e.g. Pt/TiO2 /Pt.
Jeong et al regarded a programmed compliance current in
the electroforming as the factor determining switching type
in Pt/TiO2 /Pt [103]. Low compliance currents (<0.1 mA)
activated bipolar switching rather than unipolar switching,
whereas high compliance currents (>1 mA) led to unipolar
switching [103]. Moreover, programming higher compliance
currents for set switching of the bipolar switching led to a
bipolar-to-unipolar transition. These observations suggest that
higher power dissipations resulting from higher compliance
currents might activate unipolar switching.
Electroforming into bipolar switching may be a process
introducing asymmetric interfaces in a two-terminal switching
cell, which are beyond the asymmetry due to asymmetric
electrodes, i.e. different TE and BE. Thus, the electroforming
may take one of the two interfaces as an active interface,
depending on the polarity of the electroforming voltage.
The interface may be electrochemically active so that redox
reactions, e.g. equations (1)–(4), taking place in the vicinity
of the interface are probably responsible for the subsequent
bipolar switching. Indeed, in a symmetric Pt/TiO2 /Pt cell, it
has been reported that the polarity of the electroforming voltage
determines the consequent bipolar switching behaviour,
whether eightwise or counter eightwise [58].
4. Resistive switching materials and mechanisms
Resistive switching is observable in various functional
materials, e.g. dielectric, ferroelectric, ferromagnetic and
semiconducting materials, which are basically oxides and
higher chalcogenides. Most switching materials show
filamentary-type switching behaviour. Non-filamentary-
type switching has also been observed in a few systems.
Mechanisms for filamentary- and non-filamentary-type
switching phenomena have not been clarified, although
up to now some experimental evidence supporting several
hypotheses has been revealed. In the following sections, we
survey various switching materials categorized into oxides
(section 4.1), higher chalcogenides (section 4.2), and carbon-
based and other materials (section 4.3). In section 4.4, several
mechanisms for resistive switching will be reviewed.
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D S Jeong et al
4.1. Resistive switching in oxides
4.1.1. Binary TMOs. Resistive switching and negative
differential resistance phenomena in binary TMOs, e.g. TiO2
[36], NiO [104] and Nb2 O5 [105], were already reported in
the 1960s. Although some related publications had been
published following these early findings, vigorous research
had not been performed until 2000, when several researchers
initiated active investigations on resistive switching materials
for RRAM application. Diverse TMOs, e.g. period 4 element
oxides such as TiO2 [17, 98, 103], VO2 [106], Cr2 O3 [107],
MnOx [108], FeOx [109], CoOx [110], NiO [111, 112] and
Cux O [100], period 5 element oxides such as Nb2 O5 [113],
and period 6 element oxides such as TaOx [49, 114] and
WOx [115–118], have been found to show characteristic non-
volatile resistive switching behaviour. The d block element
oxide ZnO that does not belong to the TMO category also
appears to be resistance-switchable [119]. Some binary TMOs
such as TiO, VO, MnO, FeO, CoO and NiO are regarded
as Mott insulators exhibiting Mott transitions (insulator-to-
metal transitions) [120–122]. However, the Mott transition is
attributed to a purely electronic phenomenon due to electron–
electron correlation, so that it differs from the microstructure-
or defect-related resistive switching discussed in this review.
We will review binary TMOs in periods 4, 5 and 6 in the
sequence of their atomic numbers. The first element among the
transition metals in the periodic table is Ti. This element has
been most widely investigated. Argall’s first finding in 1968
did not tell the polarity of the applied switching voltage, so
that the observed switching could not be classified as unipolar
or bipolar. In 2007, almost 40 years after the first report,
Jeong et al found bipolar switching behaviour in Pt/TiO2 /Pt
cells and the coexistence of bipolar and unipolar switching
behaviours [103]. Recently, researchers at Hewlett-Packard
labs have found ‘the missing circuit element’ memristor (the
fourth passive circuit element that was predicted theoretically
nearly 40 years ago [123]), which triggered great interest in the
application of TiO2 -based memristors to RRAMs, as well as
synapse-mimic analogue switches for neuromorphic systems
[124–128].
When one looks at the phase diagram of V–O compounds,
it can be seen that the phase diagram is almost identical to that
Rep. Prog. Phys. 75 (2012) 076502
Figure 12. Threshold switching (volatile) curves of a VO2 film on
an oxidized Si substrate. The measurement was done using a CAFM
at 293 K. The I –V curve at the first voltage application cycle (black
solid line) shows a higher threshold voltage than the following
cycles. This threshold voltage at the first cycle has been named the
‘training voltage’ by Kim et al [129]. Reprinted with permission
from [129]. Copyright 2010, American Institute of Physics.
of Ti–O compounds. The phase diagram of V–O compounds
also includes the Magnéli phases (Vn O2n−1 ). In spite of
this similarity, the resistive switching of VO2 exhibits mono-
stability [129–131]. Mono-stable resistive switching, often
called ‘threshold switching’, also shows set switching that
leads to the LRS at a certain voltage (Vset ). As long as the
applied voltage is higher than a certain voltage (Vreset ) (which
is lower than Vset in general as shown in figure 12), the LRS
can be retained. However, as soon as the applied voltage falls
below Vreset , the resistance is switched back to the HRS, i.e.
no memory effect. Typical I –V curves of threshold switching
are shown in figure 12 [129].
A first threshold switching cycle is known to obviously
exhibit a higher Vset than the Vset of subsequent cycles (see
figure 12). Kim et al have defined Vset of the first cycle as
the ‘training voltage’ [129]. A training voltage may be for
the initialization of the following threshold switching. In this
sense, this voltage perhaps acts as an electroforming voltage
for bi-stable resistive switching. The threshold switching
has been found to involve CFs formed in insulating VO2 ,
which connect the two electrodes of a threshold switch
[106, 129, 131]. However, the formed CFs are supposed to
disappear when the applied voltage falls below Vreset . The
nature of the CFs has been suggested in some literature, for
instance, a high-temperature-induced metallic phase [131], a
non-stoichiometric VO2 phase due to the drift–diffusion of
oxygen ions [129], and Magnéli phases [129].
Resistive switching in Cr2 O3 has rarely been investigated
thus far. Chen et al have looked at bipolar switching in a
Cr2 O3 film with Pt and TiN electrodes [107]. Since another
transition metal compound (TiN) was used as an electrode, the
switching likely arose from the TiN electrode or the interfacial
layer between the TiN and Cr2 O3 layers. As a matter of fact,
a Cr2 O3 film sandwiched between inert Pt electrodes (with no
interfacial layers) did not show resistive switching [132].
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D S Jeong et al
MnOx and FeOx are regarded as unipolar switching
materials [108, 109]. When they are sandwiched between Pt
TE and BE, they show bi-stable unipolar switching behaviour.
For MnOx , using asymmetric electrodes (Pt and Al) enhances
the stability of unipolar switching [108].
Shima et al have investigated non-stoichiometry effects
on the unipolar switching of initially hyper-stoichiometric
CoO [111]. In Pt/CoO/Pt cells, both pristine and HRS
resistances were found to decrease as post-annealing time in
ambient oxygen increased [111]. This possibly implies that the
oxidation of hyper-stoichiometric CoO increases the number
of free electronic carriers (holes) by equation (4) because the
non-stoichiometry of CoO arises from cobalt vacancies [60].
When a Pt/CoO/Pt cell was post-annealed in ambient oxygen
for 60 s, it became so leaky that no electroforming and no
consequent unipolar switching were observed. Moreover, it
was confirmed that the phase transition from Co3 O4 to CoO
occurred when Co3 O4 was reduced by annealing [111].
NiO systems with/without dopants are regarded as Mott
insulators, and their resistance-change phenomena have been
extensively studied in the scope of the Mott transition [121].
In addition to the Mott transition, unipolar switching in NiO
has been widely and globally investigated for its application
in RRAMs. Indeed, NiO is one of the most widely studied
materials for unipolar-switching-type RRAMs. As a result,
some methods to enhance the reliability and to reduce the reset
current have been suggested [112, 133, 134]. Just as with most
resistive switching materials, electroforming is necessary to
trigger unipolar switching in NiO. The suggested mechanisms
for the unipolar switching barely differ from the ‘universal’
one and still involve the formation and rupture of CFs. The
CFs are estimated to be composed of metallic Ni that is phase-
separated from the NiO mother matrix. By means of TEM
analysis, Park et al observed Ni phase segregating at grain
boundaries in the NiO film of an electroformed cell [135].
CuOx is also a unipolar switching material [100, 136–138].
Recently, Yajima et al have identified the formation of a CF
during electroforming in a Pt/CuO/Pt lateral switching device
as discussed in section 3.4 [100]. The authors studied the
Joule-heat-assisted diffusion and electric-field-induced drift of
oxygen ions along the CF as a mechanism for switching [100].
Bi-stable bipolar switching in Nb/Nb2 O5 /Bi switching
cells was found by Hiatt and Hickmott in 1965 [105]. The
I –V loops in the paper represent a cells’ bipolar switching
nature. The authors pointed out the possible use of this bi-
stable switching phenomenon in memory devices. It turned
out later on that Nb2 O5 with Pt and Si electrodes also show
unipolar switching behaviour [139]. Either Nb2 O5 itself
may have both unipolar and bipolar switching natures, or
the activation of a particular switching type may depend on
the electrode materials. Resistive switching and negative
differential resistance phenomena in TaOx have also been
found [140]. Recently, Yang et al have demonstrated the
excellent endurance of bipolar switching in Ta/TaOx /Pt cells,
which worked for over 1010 cycles [49].
Very recently, ‘intrinsic’ bipolar switching in hypo-
stoichiometric WO3 has been under investigation by several
researchers in the Far East [115–118]. At the industry level,
Rep. Prog. Phys. 75 (2012) 076502
WO3 may be the best choice as a switching material for
its compatibility with conventional tungsten via structure in
semiconductor devices. WO3 has been demonstrated as a
solid electrolyte in ECM cells [141]. In this case, WO3 is
a cation-diffusion medium rather than an intrinsic switching
material. Similar to Ti–O and V–O compounds, W–O
compounds are able to accommodate oxygen deficiency by
forming crystallographic shear planes, i.e. Magnéli phases.
However, microscopic investigations seeking the correlation
between microstructure and resistive switching have not yet
been conducted. WO3 has been known to exhibit bipolar
switching with various combinations of TE/BE, e.g. Pt/W
[116], Au/(fluorine-doped tin oxide (FTO)) [118] and Al/FTO
[115]. When W is employed as a BE material, WO3 can
be formed by thermal oxidation without additional deposition
processes. Kim et al have demonstrated excellent switching
reliability in Pt/WO3 /W cells scaled down to 50 nm [142].
4.1.2. Perovskite-type complex TMOs. Perovskite-
type complex TMOs exhibit various functionalities, e.g.
paraelectric, ferroelectric, colossal magnetoresistance (MR),
multiferroic, and, of course, resistive switching. As briefly
stated earlier, perovskite-type paraelectric Cr-doped SZO is
one of pioneer materials [15, 40]. Several other paraelectric
perovskite-type complex TMOs such as STO [76, 143] and
(Ba,Sr)TiO3 (BST) [144, 145] have also been found to exhibit
resistive switching.
Resistive switching in ferroelectric complex TMOs is
believed to have first been reported in Au/PTO/LSCO
ferroelectric Schottky diodes by Blom et al [39]. They
believed that ferroelectric switching alters the carrier-depletion
width and thus the conductivity of delocalized electrons in
PTO. Another type of ferroelectric-related resistive switch is
ferroelectric tunnel junction (FTJ) [146, 147]. In an FTJ, the
tunnelling matrix element, i.e. tunnelling probability, varies
with the ferroelectric switching so that ferroelectric-resistive
switching can be achieved. BaTiO3 (BTO)/SrRuO3 (SRO)
[148] and PZT/Lax Sr 1−x MnO3 (LSMO) [149] systems
without TE have recently shown FTJ behaviour, which were
measured using conductive atomic force microscope (CAFM).
Discussions on FTJs in detail will be given in section 4.4.4.
Memories based on tunnel junctions with ultrathin
ferroelectric barriers would enable non-destructive resistive
read-out, contrary to the sub-micrometre thick ferroelectric
films currently used in FRAMs with destructive capacitive
read-out. Recent studies on highly strained BTO observed
the electroresistance effect that scaled exponentially with
ferroelectric film thickness, reaching ∼75 000% at 3 nm [150].
This resistive read-out of the polarization state can also result
in density beyond the gigabit regime through its influence on
the tunnel current.
In 2000, the MR material PCMO was found to exhibit
EPIR behaviour [16]. This finding was somewhat surprising
because the applied electric field was solely able to toggle
the resistance states at room temperature; the application of
a magnetic field was unnecessary. Nian et al identified that
the EPIR effect arises from the oxygen vacancy migration and
redistribution rather than the MR effect [151].
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D S Jeong et al
In the case of resistive switching in multiferroics, the
diode-like forward-to-backward current ratio can exceed
100 : 1, parallel or antiparallel to the polarization; some act as
ferroelectric Schottky-diodes where the Schottky barrier height
(SBH) at the metal/multiferroic interface is altered by the
remnant polarization. However, the situation is complicated.
The mechanism is neither intrinsic nor clearly understood even
though there are a number of reports on resistive switching in
multiferroics [152–155]. Very recently, these devices have
had a breakthrough using multiferroic BFO; switched current
densities of >5 A cm−2 were achieved, which is about 1000×
greater than those in PZT, and sufficient for any memory sense
amplifier to discriminate +P from −P, i.e. ‘1’ from ‘0’. Very
good retention was another breakthrough realized (>3 months
in 720 specimens tested) [156]. And perhaps most important,
the fabrication process is CMOS-compatible with a real TE,
rather than a CAFM tip.
4.1.3. Large band gap high-k dielectric oxides. Owing to the
need for high-k and low leakage current materials in DRAM
and CMOS, high-k dielectrics of large band gaps (highly
insulating) have been intensively investigated. There have
been some efforts to detail the nature of resistive switching
in such dielectrics including Al2 O3 [34, 157–163], and Gd2 O3
[164–166]. Al2 O3 films are employed in switching cells in
various ways: Al2 O3 in contact with (i) inert electrodes, e.g.
Pt and Au (ii) Al electrodes, and (iii) in other oxygen-reactive
electrodes, e.g. Ti.
(i) Al2 O3 films with some inert electrode materials, for
instance, Pt/Al2 O3 /Ru and Au/Al2 O3 /Au, exhibit unipolar
switching [157, 163]. However, a comparative study on
the unipolar switching behaviour of Pt/Al2 O3 /Ru and
Pt/TiO2 /Ru shows poor stability of set and reset switching
voltages as well as low HRS-to-LRS ratios of Pt/Al2 O3 /Ru
compared with Pt/TiO2 /Ru [157].
(ii) When Al electrodes are used in Al2 O3 -based switching
cells, both unipolar and bipolar switching natures could be
observed. Karthäuser et al have found bipolar switching in
ZnO/Al2 O3 /Al cells with 50 nm thick Al2 O3 films [161].
Anodic aluminium oxide (AAO) has also been identified
as a resistive switching material [158, 159]. Interestingly,
Kato et al and Yalishev et al respectively reported unipolar
switching and bipolar switching in Ag/AAO/Al cells.
This may mean that AAO has both unipolar and bipolar
switching natures. However, as discussed in section 2.1,
set and reset switching occurring in different quadrants
on an I –V plane do not necessarily indicate bipolar
switching. One should therefore confirm the polarity
dependence of resistive switching in AAO carefully before
drawing the conclusion that unipolar and bipolar switching
coexist in this system.
(iii) There have been some publications on resistive switching
phenomena in Al2 O3 films in contact with a Ti electrode,
which is oxygen-reactive [160, 167]. Sometimes, the Ti
electrode is formed on an Al2 O3 film using an ex situ
deposition process. An Al2 O3 film exposed to humid air
most likely forms a thin aluminium hydroxide layer at
the surface [168]. The aluminium hydroxide layer may
Rep. Prog. Phys. 75 (2012) 076502
turn to an Al2 O3 layer with oxidizing the subsequently
deposited oxygen-reactive metal layer [169]. Therefore,
the Ti electrode grown on the aluminium hydroxide layer
is probably oxidized to either TiO2 or lower Ti oxide.
As discussed earlier, TiO2 and lower Ti oxides are also
resistive switching materials, so that the interfacial Ti
oxide layer in this switching cell may contribute to
resistive switching.
Mechanisms for resistive switching in Al2 O3 have been
proposed including the phase transition of Al2 O3 due to Joule
heat [162], the trapping and detrapping of electronic carriers
[162], and the formation and rupture of CFs [163].
Gd2 O3 is also a resistive switching material. Cao et al
have successfully measured unipolar switching in Pt/Gd2 O3 /Pt
cells [164]. They used a Gd2 O3 film grown in oxygen-
deficient atmosphere, and thus the film was initially quite
leaky. The leaky switching cells worked well even without
electroforming. However, a Gd2 O3 film deposited under high
oxygen pressure was highly insulating, so that electroforming
is required for subsequent resistive switching [164]. Not
only Pt but also other electrode materials such as Ti and
transparent indium-tin-oxide (ITO) were used in Gd2 O3 -based
switching cells [165, 166]. ITO/Gd2 O3 /ITO cells are optically
transparent, and thus they can be basic elements of transparent
RRAMs. An interesting point is that ITO/Gd2 O3 /ITO cells
represent the coexistence of unipolar and bipolar switching
natures. In terms of stability, bipolar switching is preferable
to unipolar switching [166]. However, the HRS-to-LRS ratio
of bipolar switching is much smaller than unipolar switching.
4.2. Higher chalcogenides
This section is dedicated to resistive switching in higher
chalcogenides, i.e. chalcogenides excluding oxides. This
review will not cover phase-change-type higher chalcogenides
because they fall into the category of PCMs.
A number of higher chalcogenides, e.g. sulfides, tellurides
and selenides, are known as resistive switching materials. We
refer to these higher chalcogenides as ‘resistive switching
materials’ rather than PCMs because their behaviour cannot
be understood in terms of phase-change. Some amorphous
sulfides, e.g. As2 S3 and Sb2 S3 [170], and crystalline sulfides,
e.g. CdS and PbS [171], exhibit bipolar switching, known
as ‘polarized memory effect’. The phase-change results
in unipolar switching as the Joule heat bringing about the
phase-change hardly depends on the polarity of the applied
voltage/current. Therefore, this bipolar switching should be
distinguished from phase-change-type switching. Doughnut-
shaped explosive spots over the surface of these sulfides were
observed after set switching as resistive switching oxides [170].
Resistive switching characteristics of amorphous tel-
lurides, e.g. In2 Te3 and As2 Te3 [170, 172], and crystalline
tellurides, e.g., ZnTe [173], have been reported in some pub-
lications. A mechanism for the set switching of In2 Te3 was
proposed to be the electrothermal effect [172]. However, the
switching-type (bipolar or unipolar switching) was not eluci-
dated in this paper. As2 Te3 showed bipolar switching, but it
18
D S Jeong et al
was very unstable [170]. Single-crystalline ZnTe films grown
on Ge substrates also exhibited bipolar switching [173].
Jeong et al have reported unipolar switching found
in amorphous selenides, GeSe and GeSex Te1−x [174].
Filamentary conduction in the LRS was observed, implying
that CFs were involved in the observed unipolar switching.
Amorphous GeSe also exhibits volatile resistive switching, i.e.
threshold switching [175], meaning the coexistence of volatile
and non-volatile (unipolar) switching in this system. Se itself
appears to be a bipolar switching material as Matsushita et al
have reported [176]. However, since the authors used diffusive
Cu electrode which is often used in ECM cells [14], it is not
certain whether the switching was attributed to the Se film or
the electrode. Okushi et al have shown that single-crystalline
ZnSe films on Ge substrates show bipolar switching [52].
Recently, Mott insulators AM4 X8 (A = Ga, Ge; M = V,
Nb; X = S, Se) have been found to exhibit the coexistence of
volatile and non-volatile resistive (unipolar) switching [177].
The mechanism has been speculated to be an electric-field-
induced insulator-to-metal transition without changes in the
microstructure of the Mott insulators. These phenomena were
considered from a purely electronic point of view. However,
this point of view is controversial because of a voltage–time
dilemma [178]. This will be discussed in detail in section 4.4.3.
4.3. Carbon-based materials and other materials
Several recent papers have reported resistive switching in
graphene oxide films [179, 180]. It should be noted that these
systems have either (i) diffusive electrodes such as Cu, or (ii)
oxygen-reactive electrodes such as Al.
(i) In this case, most insulating films allowing Cu ions
to diffuse through them may show bipolar switching
attributed to the formation and rupture of Cu CFs.
Therefore, in this system the graphene oxide film serves
as a cation diffusion medium and a spacer separating
the two electrodes so that the observed bipolar switching
cannot be regarded as an intrinsic property of the graphene
oxide film.
(ii) Resistive switching in this case is most likely attributed to
an interfacial Al2 O3 layer, generally AlOx , between the
Al electrode and graphene oxide.
In the 1970s, the ‘polarized memory effect’ in amorphous
carbon films was investigated, but is now known as bipolar
switching [181, 182]. The bipolar switching could be observed
in a carbon-based cell employing an Al electrode as at
least one of the two electrodes [182]. Otherwise, neither
electroforming nor switching was achieved [182]. Similar to
the aforementioned bipolar switching in graphene oxides with
Al electrode, this switching effect is perhaps attributed to the
resistive switching of the interfacial AlOx layer. A diamond-
like carbon film with W electrode has also been studied as a
unipolar switching material [183]. The suggested mechanism
is the formation and rupture of conductive sp2 -type CFs in the
insulating sp3 -type carbon matrix.
Several organic materials, e.g. Rose Bengal [161],
2,3-dichloro-5,6-dicyano-1,4-benzoquinone [184], p-phen
ylenevinylene [185], conjugated copolymer containing
Rep. Prog. Phys. 75 (2012) 076502
fluorine and chelated europium complex [186], also exhibit
resistive switching natures and are potential candidates for
RRAMs. However, many switching organic materials are very
often in contact with Al electrodes [161, 184, 185]. In fact,
Karthäuser et al have pointed out that switching cells utilizing
Al electrodes probably show the resistive switching effect of
the interfacial AlOx layers rather than these organic films [161].
4.4. Mechanisms for resistive switching
We overviewed a number of resistive switching materials in
the previous sections. In spite of the variety of possible
switching materials, the number of materials that are actually
responsible for resistive switching seems to be not as many as
that of nominal switching materials. Namely, second phases
that are interfacial, unintentionally formed and known to be
resistance-switchable by themselves are perhaps in charge of
the resistive switching in many systems, as discussed in the
previous section. However, there are still too many switching
materials left to figure out the mechanism of each. Fortunately,
there is the general and system-independent consensus that
CFs play a key role in resistive switching. Of course, there are
exceptions, i.e. switching systems showing scaling resistance
with pad size. A few of these are, e.g., Fe-doped STO [51], Nb-
doped STO [187] and WO3 [188], implying non-filamentary
conduction and switching. Non-filamentary switching is
sometimes known as interface-type switching [45]; it does
not involve electroforming and both set- and reset-switching
behaviours are gradual rather than abrupt, unlike filamentary
switching cases.
It is worth noting that filamentary conduction does not
necessarily lead to non-scaling resistance because resistance
scaling is a matter of the distributional uniformity of CFs.
Consider the uniform distribution of CFs over the pad area of
a switching cell. In this case, the resistance of the cell scales
with the pad size, although the conduction is still attributed
to the CFs. Therefore, one cannot conjecture conduction and
switching types from pad-size dependence. In the case of non-
scaling resistance of a switching cell, a few CFs whose number
is not proportional to the pad size probably contribute to the
conduction. Indeed, this hypothesis is quite probable because
the growth of the CFs probably follows the winner-take-all
procedure [57] as discussed in section 3.
The interface between an electrode and a switching layer
is perhaps of great importance for the conduction in the
bi-stable states and the switching between the states. The
interfacial resistance of several switching systems appears
to control the overall resistance and its change likely leads
to resistive switching [189–192]. Therefore, it is worth
discussing some basic theories on the interface between an
electrode and a switching layer with particular emphasis on
hypo-stoichiometric TiO2 .
4.4.1. Interface between electrode and switching materials.
Many switching oxides including binary and complex TMOs
are solid electrolytes (SEs) where not only electronic carriers
but also mobile ions or ionic defects contribute to the
current transport. In hypo-stoichiometric oxides, delocalized
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D S Jeong et al
electrons and oxygen vacancies, or cation interstitials,
depending on the dominant defect formation reaction (either
equation (1) or (2)), serve as major charge carriers, whereas
in hyper-stoichiometric oxides, delocalized holes and cation
vacancies, or oxygen interstitials, depending on the dominant
reaction (either equation (3) or (4)).
It is known that the I –V behaviour of metal/SE/metal
cells heavily relies on the electrode materials [145, 193, 194].
This implies the importance of property of the anode/SE (n-
type) and cathode/SE (p-type) interface for electronic carrier
injection. The Schottky barrier formed at the metal/SE
interface plays an important role in the electronic transport,
mostly injection through the SBH. Ideally, the SBH is defined
as the difference between the electron affinity of the SE and
work function of the metal. The SBH is therefore supposed to
be proportional to the work function of the metal. However,
in reality there may be an interfacial layer between the metal
and SE, which is equivalent to a thin-slab-shaped capacitor.
A certain voltage drop through the layer occurs, leading to
a deviation of the SBH from the ideal value as suggested by
Cowley and Sze [195].
Yang et al identified a role of the interfacial layer in
the current injection through the metal/SE interface in TiO2
in contact with various electrode metals [193]. The SBH
at the metal/TiO2 interface is strongly affected by the oxide
formation free energy, rather than the work function, of the
metal as shown in figure 13 [193]. This suggests that the TE
metal works as a reducing agent, resulting in the reduction
of TiO2 . Moreover, a lower free energy of oxidation of a
deposited metal results in a lower free energy of an oxygen
ion transfer reaction between the deposited metal and TiO2 .
The reduction of TiO2 may introduce oxygen vacancies in
the vicinity of the TiO2 surface while keeping the original
crystal structure. Otherwise, the reduction may lead to the
phase transition of TiO2 into its lower oxide. Either method
results in the lowering of the interfacial resistance so that the
overall resistance decreases.
The Helmholtz and diffuse double layers need to be
employed in a description of metal/SE interface [196–198].
When a metal/SE junction is formed, the electron transfer
between the metal and SE takes place due to an inherent
difference in the electrochemical potential of electrons
between the metal and SE. The electron transfer causes space
charge leading to an interfacial dipole layer and is equivalent
to a capacitor, as illustrated in the schematic in figure 14.
Owing to the very high electron concentration in the metal,
the electric field screening length on the metal side is very
short. On the SE side, however, the electric field is screened
by both electronic carriers and ions/defects through the diffuse
double layer. The number of charged carriers in the SE is
generally not as great as that of electrons in the metal so
that the screening length is much longer. The ions on the
Helmholtz plane are responsible for the first screening and the
electronic carriers and ions/defects in the diffuse double layer
the second screening [196, 197]. The diffuse double layer in
SE differs from that in the liquid electrolyte where no electronic
carriers exist. Note that in SE the diffuse double layer of the
conventional meaning may not be present because of the very
Rep. Prog. Phys. 75 (2012) 076502
Figure 13. Resistances at a read-out voltage of ±1 V of several metal/TiO2 /metal cells with the same Pt BEs and various TEs, Ti, W, Ni, Pt,
Ag and Au. The measured resistance values are plotted with respect to (a) the work function of the TEs and (b) the oxide formation free
energy of the TEs. Reproduced with permission from [193]. Copyright 2011, Springer.
Figure 14. (a) Schematic of metal/SE interface where the metal is
positively charged. The corresponding (b) charge concentration, (c)
electrostatic potential and (d) electron energy profiles through the
junction are illustrated. The electric field screening length in the
metal is exaggerated.
low mobility of ions/defects in SE as well as electronic carriers
partly taking over the role of ions/defects in the electric field
screening.
A higher concentration of ions/defects in the vicinity of
the metal/SE interface probably leads to a higher voltage drop
20
D S Jeong et al
through the Helmholtz layer, and thus the SBH, which the
electrons injecting from the metal see, decreases [53, 199].
The numerical calculation of I –V curves for Pt/TiO2 /Pt
junctions, where TiO2 has various profiles of oxygen vacancy
concentration, elucidated the aforementioned relationship
between the SBH and defect (oxygen vacancy) concentration
[199]. As shown in figure 15, the calculation results
indeed identify the change of the SBH with respect to the
concentration of oxygen vacancies in the diffuse double layer.
4.4.2. Conduction mechanisms in the bi-stable states.
An equivalent circuit of a switching cell embedding a CF
is illustrated in figure 16(a). This equivalent circuit is
oversimplified for easy understanding. Electronic current flow
along the M1/I/M2 junction in the equivalent circuit can be
divided into injection, bulk and ejection currents. The three
serial resistors, RIM1 , RIB and RIM2 , are respectively equivalent
to these three current terms. Of course, depending on the
polarity of the applied voltage and major electronic carrier type,
RIM1 and RIM2 can exchange their roles. However, it should
be noted that the overall resistance cannot be easily described
by these independent resistors [200]. Unlike the M1/I/M2
junction, the three resistors, RCFM1 , RCFB and RCFM2 of the
M/CF/M junction in figure 16(a) are perhaps independent of
each other. Because the short electric field screening length
caused by the high concentration of electronic carriers in the
CF does not allow the distribution of the injected carriers to tail
towards the bulk of the CF, the injection current hardly affects
the CF bulk resistance RCFB .
When the resistance of the CF (RCFM1 + RCFB + RCFM2 )
is much lower than that of the rest of the volume, i.e.
RIM1 + RIB + RIM2 , the only current flowing through the CF is
externally measured. In spite of the very high conductivity
of the CF compared with the pristine matrix, if the cross-
sectional area of the CF is small enough to make its resistance
comparable to or even higher than that of the pristine matrix,
Rep. Prog. Phys. 75 (2012) 076502 D S Jeong et al

Figure 15. (a) Calculated I –V curves for various profiles of oxygen vacancy concentration in TiO2 in a one-dimensional Pt/TiO2 /Pt
junction. A voltage is applied to the right Pt electrode while the left one is grounded. The oxygen vacancy concentration in the left (right)
diffuse double layer was assumed to be 1.28 × 1020 cm−3 (1.28 × 1020 cm−3 ) for A1, 1.28 × 1020 cm−3 (5 × 1020 cm−3 ) for A2,
5 × 1020 cm−3 (1021 cm−3 ) for A3, 2 × 1021 cm−3 (1021 cm−3 ) for A4, 2 × 1021 cm−3 (5 × 1021 cm−3 ) for A5, 8 × 1021 cm−3 (5 × 1021 cm−3 )
for A6, 8 × 1021 cm−3 (1022 cm−3 ) for A7, respectively. (b) Calculated electron energy band diagram in the Pt/TiO2 /Pt junction for A7 at
0 V. φm , V (0), Evac , χTiO2 , EF and EC denote the work function of Pt, a voltage drop through the left Helmholtz layer, the vacuum level, and
the electron affinity, the Fermi level, and the conduction band minimum of TiO2 , respectively. Reprinted with permission from [53].
Copyright 2009, Forschungszentrum Jülich.

the current through the CF is not prominent. According
to Münstermann et al, an example of this case has been
recently found in an Fe-doped STO film on a Nb-doped STO
[51]. They identified the coexistence of filamentary and non-
filamentary conduction behaviours in the system, as shown in
figure 16(b). Moreover, they have also identified that non-
filamentary conduction and switching can be dominant or
at least comparable to filamentary conduction and switching
so that the non-filamentary event is measureable in the
10 × 10 µm2 MIM junction.
For TiO2 and BST, it can be seen that (i) the LRS of
unipolar switching shows metallic behaviour, whereas the
other states ((ii) the HRS of unipolar switching and both
(iii) LRS and (iv) HRS of bipolar switching) show thermally
activated conduction behaviour with particular activation
energies [103, 201]. This implies that for the last three states,
(ii), (iii) and (iv), the electronic conduction along CFs takes
place by overcoming energy barriers whose heights correspond
to activation energies. By analogy with the conduction in
pristine MIM junctions as discussed in the previous section,
the energy barrier for the three states, (ii), (iii) and (iv), may
be placed at the cathode/CF interface; this means RCFM1 or
RCFM2 is a dominant resistor, depending on the polarity of the
applied voltage. However, no indication obviously identifying
the interface-controlled conduction has been experimentally
observed so far.
There has been indirect evidence pointing out what
resistor(s) is responsible for resistive switching in several
switching cells. For instance, Kim et al have noticed anode-
induced unipolar switching in Pt/TiO2 /Pt cells, suggesting that
the anode interface is an active switching component [192].
For bipolar switching in Pt/TiO2 /Pt cells, Jeong et al indirectly
found that both interfacial resistors of a CF(s) (RCFM1 and
RCFM2 ) can be active, and each resistor is in charge of one of the
two different bipolar switching behaviours, i.e. eightwise and
counter eightwise switching curves [190]. Moreover, the two
different behaviours can simultaneously take place depending
on the range of the applied voltage.
However, the interface responsible for the unipolar
switching in NiO is controversial. Kinoshita et al have
estimated the anode/CF interface to be in charge of unipolar
switching [191]. This conclusion was drawn from the
observation that the HRS, programmed by applying a positive
voltage to the surface of the NiO film, was vulnerable to
sputtered Pt atoms on the surface. This may suggest that the
programmed region was located in the vicinity of the anode.
In contrast, Kim et al have conjectured that unipolar switching
takes place at the cathode from the results of switching
measurements on two series of NiO resistors [202].
Baikalov et al performed switching measurements on
PCMO films exhibiting bipolar switching [189]. In their
experiment, many switching cells were in series connections,
and each cell consisted of Ag/PCMO/YBa2 Cu3 O7 . Basically,
the measurement configuration was the same that Kim et al
used for TiO2 unipolar switching measurements [192]. It
turned out that the Ag/PCMO interface was responsible for
the resistance change, although they did not clarify whether
the interface was the anode or cathode.
4.4.3. Mechanisms for unipolar switching. Up to now
many different mechanisms for resistive switching have been
introduced since the 1960s. Several prototypical models were
already suggested in the 1960s and 1970s by Hickmott [68, 69],
Simmons and Verderber [70], Barriac et al [71] and Dearnaley
et al [74]. These models are universal rather than material-
specific, and thus they can be employed for many different
switching materials. Note that all these models deal with only
unipolar switching.
Hickmott [68, 69], and Simmons and Verderber [70] have
attempted to explain N-shaped negative differential resistance
effects, i.e. reset switching, in terms of the interaction between
electronic carriers and immobile impurities leading to localized

21
Rep. Prog. Phys. 75 (2012) 076502
Figure 16. (a) Schematic of a CF embedded in an insulating
background and placed between electrodes (M1 and M2). Possible
resistance components in the cell are illustrated in the figure.
RCFM1 (RCFM2 ) and RIM1 (RIM2 ) denote the resistances of the interface
between the CF and electrode M1(M2) and between the insulating
matrix and electrode M1(M2), respectively. RCFB and RIB mean the
resistances of bulk of the CF and insulating matrix, respectively. (b)
CAFM-measured morphology and current maps of a 500 nm thick
Fe-doped STO film on a Nb-doped STO substrate. This junction
initially had Pt TE, but the TE was removed after electroforming for
the CAFM measurement. The crater in the dotted green ellipse
appears to correspond to the CF in figure. (a), whose current is
governed by the three series resistors (RCFM1 + RCFB + RCFM2 ). The
current change of the area is in the orange ellipse but the green one
is perhaps attributed to a change in RIM1 + RIB + RIM2 . Reproduced
with permission from [51]. Copyright 2010, Wiley-VCH.
states or an energy band in the band gap. These mechanisms
are for unipolar switching, although the authors did not
communicate that in the papers. They regarded the resistive
switching to be driven by the change of electronic configuration
in the band gap without any microstructural change. Hickmott
pointed out that a decrease in the conductance in reset
switching is a result of a decrease in the number of charged
impurity centres [68, 69]. Simmons and Verderber compared
the electrochemical potential of electrons in the cathode with
the impurity band maximum in the neutral region of the
switching layer, and tried to figure out the change in the
electronic conduction with respect to the differences between
them [70].
Electric-field-induced insulator-to-metal transition in
Mott insulators is another electronic mechanism. Recently,
Cario et al concluded that AM4 X8 Mott insulators (A = Ga,
Ge; M = V, Nb; X = S, Se) exhibit electric-field-induced
insulator-to-metal transition from the fact that no change in
the microstructure of the Mott insulators during switching
operations was observable [177].
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D S Jeong et al
Regarding the voltage–time dilemma suggested by
Schroeder et al [178], ‘purely electronic’ passive non-volatile
switches (two-terminal devices) hardly satisfy both long
retention and short switching times. In a purely electronic
passive switch, particular electronic states written by the
applied voltage/current will rapidly undergo relaxation as soon
as the voltage/current disappears, and hence the states cannot
be retained. Of course, the relaxation is a matter of a relaxation
time constant so that if the constant is very large, a retention
time of several years can be guaranteed. However, one should
bear in mind that in purely electronic mechanisms, switching
and retention are related to paired processes, i.e. one process
is the reverse of the other. For instance, in Hickmott’s model,
the reset switching and the retention of the consequent HRS
are related to electron trapping and detrapping, respectively
[68, 69]. The trapping and detrapping are related to each
other by detailed balance [203], and thus if a time constant
of the detrapping is long, so is that of the trapping. Therefore,
fast switching and good retention are inconsistent with the
aforementioned electronic features.
Generally, a voltage/current applied to a switching cell
leads to electrical polarization or charging. Unless the
polarization or charging is not mediated by microstructural
change, the removal of the applied voltage/current immediately
causes discharging. A time constant of the charging is
comparable to that of the discharging. Therefore, short
switching times in general imply short retention times, which
is not consistent with resistive switching features.
Concerning the aforementioned features of the electronic
mechanisms, the electronic processes may result in mono-
stable volatile switching, i.e. threshold switching. For
instance, the double-injection model by Adler et al provided
a good explanation for threshold switching in amorphous
chalcogenides without bringing about the voltage–time
dilemma [204].
Filamentary conduction and switching was first suggested
by Dearnaley [56]. He did not specify CFs at the atomic
level although he suggested some possible models such as –
Si–O–Si– chains in SiOx [56] and more generally –M z+ –M z+ –
chains [205]. His model is prototypical and the current models
for unipolar switching do not go far out of its scope. In this
model, the reset switching is a result of the rupture of the CFs in
the insulating matrix by Joule heat, while a mechanism for set
switching is assumed to be the recovery of the ruptured CFs.
At present, the mechanism based on these processes is called
the fuse–antifuse type [13]. The fuse–antifuse mechanism is
still most commonly used to describe unipolar switching in
numerous switching systems. However, this mechanism is
still far from realization at the atomic level.
Waser et al have referred to unipolar switching in TMOs
as thermochemical memory (TCM) switching [14]. The
TCM effect is attributed to the temperature-induced change
of valence state of transition metal ions. In this model, the
transitions into lower oxide phases for all binary TMOs are
spontaneous in a wide temperature range at the standard state
[14]. This is shown in the Ellingham diagram. Before the
introduction of the TCM effect, Chudnovskii et al suggested
that high-to-low oxide transitions in TMOs take place during
Rep. Prog. Phys. 75 (2012) 076502
Figure 17. Free energy of oxidation of some metals and Ti lower
oxides. Reprinted with permission from [193]. Copyright 2011,
Springer.
electroforming as discussed in section 3.1 [75]. However, the
authors only took into account anodizing-grown TMOs, so that
their theory cannot be directly applied to TMOs on different
electrodes.
It is noted that the formation energy shown in the
Ellingham diagram is given per unit oxygen mass. For
instance, the TiO2 formation energy (G0f,TiO2 ) is for the
reaction, Ti +O2(g) = TiO2 , whereas the TiO formation energy
(G0f,TiO ) is for 2Ti+O2(g) = 2TiO. Therefore, the reduction of
TiO2 resulting in TiO, 2TiO2 = 2TiO + O2(g) , has a formation
energy of G0f,TiO − 2G0f,TiO2 . Indeed, this formation energy
is positive in the whole temperature range, meaning that the
reduction cannot be spontaneous at the standard state. For the
spontaneous reduction of TiO2 , other factors such as reducing
agent(s) and changes in the oxygen partial pressure should
therefore be involved. Yang et al compared the free energy
of oxidation of lower Ti oxides into TiO2 with that of several
metals into their oxide phases and found that the transition
from TiO2 to lower Ti oxides can be spontaneous depending
on the electrode metals, i.e. reducing agents, in contact with
TiO2 [193]. As shown in figure 17, for instance, the reduction
of 2nTiO2 , 2nTiO2 = 2Tin O2n−1 + O2(g) , is spontaneous in a
wide range of temperatures with reducing agents such as Ni,
W, Cr and Al. In the case of unipolar switching in TMOs with
no stable lower oxides, e.g. NiO, transition into their metallic
phases is probably preferable, and leads to metal precipitation.
The reset switching of unipolar switching is still very
mysterious. There have been several attempts to quantitatively
describe the I –V characteristics of the reset switching by
23
D S Jeong et al
means of the fuse–antifuse mechanism [206, 207]. In these
publications, the reset switching is believed to be attributed to
the dissolution of CFs owing to Joule heat. By considering
the redox and thermal diffusion of metallic elements in a CF,
Bocquet et al derived a single equation accounting for both
set and reset switching and numerically demonstrated that
the equation is able to describe both switching behaviours
depending on the initial conditions [207].
As long as a CF is assumed to be cylinder-shaped, the
hottest point is placed at the centre of the CF owing to the
heat released through the electrodes sandwiching the CF. The
centre is therefore likely to be responsible for switching if
unipolar switching is temperature-driven [206, 207]. However,
there have been several papers experimentally identifying the
interface between electrode and switching layer as a switching-
determining region, which is discussed in section 4.4.2
[191, 192, 202]. Kim et al have assumed a cone-shaped CF
to place the hottest region at the interface and found some
consistency with their experimental data [208–210].
Another thermal approach to the understanding of reset
switching has been done by Jeong et al in terms of the order-
to-disorder phase transition triggered by Joule heat [211].
They considered the reset switching as the transition from
an ordered phase (aligned conducting blocks connecting the
two electrodes) to a disordered phase (broken CF). As a
non-thermal approach to a unipolar switching mechanism,
Chae et al simulated set and reset switching based on a
random circuit breaker model [212]. The simulation results
can describe the experimental unipolar switching behaviour.
However, this model lacks the detailed physics of the circuit
breakers. Moreover, this model hardly explains the interface-
determining unipolar switching behaviour.
4.4.4. Mechanisms for bipolar switching. Although bipolar
switching was already observed in the 1960s and 1970s, it
was far from understood by that time. In 1970, Hovel [173]
attempted to employ a purely electronic mechanism related to
the trapping and detrapping of electrons, which is very similar
to the Hickmott’s model [68, 69]. In 2000, Beck et al regarded
a change in the valence state of dopants in Cr-doped SZO as a
bipolar switching mechanism [15]. Then, Rossel et al realized
that the CF formation and rupture coupled with structural
change are in charge of bipolar switching [213]. Both
LRS and HRS of Cr-doped SZO exhibit metallic resistance
versus temperature relationships [80], distinguishable from the
thermally activated conduction behaviour in TiO2 [103] and
BST [144]. Later, the change in conductivity or/and geometry
of CFs in Cr-doped SZO was regarded as a mechanism for
the switching, which is due to oxygen vacancy drift along the
applied electric field [80].
Waser and Aono have understood bipolar switching in
both binary and paraelectric perovskite-type TMOs in terms
of the anion migration effect, i.e. oxygen ion/defect migration,
and classified this switching type as the anion migration class
[13]. Later, Waser et al have suggested the more advanced
and general terminology ‘valence-change memory’ (VCM)
that can be applied to both of the anion and cation migration
classes [14]. The idea is that oxygen vacancy migration in a
Rep. Prog. Phys. 75 (2012) 076502
TMO, which is driven by the electrochemical potential gradient
of oxygen vacancies, leads to the reduction of transition metal
ions. That is, the charge neutrality condition is satisfied by the
reduction. The valence change may be assisted by the Joule
heat introduced during the ion/defect and electronic carrier
migration [214].
Set switching in a VCM cell arises from the reduction
of transition metal ions, which results in an increase in
electron population in the d-band, i.e. the conduction band.
This implies that the reduction increases the number of free
electrons and the conductivity. Reset switching can be
achieved by altering the applied voltage polarity. The altered
polarity leads to the re-oxidation of the reduced transition
metal ions, emptying the conduction band and decreasing the
conductivity. These redox reactions are thought to occur at
the active metal/SE interface(s) with the help of the Helmholtz
layer giving discrete Galvani potential distribution through the
interface [53, 199].
The VCM effect may be coupled with the change of the
SBH [45, 53, 199]. The higher the concentration of reduced
transition metal ions or oxygen vacancies in the diffuse double
layer, the lower the SBH at the interface. Therefore, VCM-type
bipolar switching is also explained in terms of the SBH change
with respect to the polarity of the applied voltage [53, 199].
Some higher dimensional defects may be involved in the
VCM effect. For instance, one-dimensional extended defects
(dislocations) in STO have been regarded to be involved in the
VCM effect [76]. Moreover, two-dimensional defects (shear
planes) in TiO2 have been found to be related to the VCM
effect, as they result in phase transition into its lower oxides
such as Magnéli phases [98, 99, 101, 214].
An electronic mechanism for bipolar switching has been
recently revisited by Kim et al [209, 215]. They regarded that
the asymmetric distribution of electron traps in TiO2 brings
about asymmetric I –V curves while bipolar switching. Space-
charged-limited conduction (SCLC) was taken as a mechanism
for the dominant conduction in the bi-stable states. In this
model, the trapping and detrapping of electrons are estimated to
occur during set and reset switching, respectively, and thus the
SCLC, strongly affected by the distribution of empty and filled
traps, exhibits resistance change with respect to the polarity of
the applied voltage.
Ferroelectric-resistive switching in a metal/ferroelectric/
metal (MFM) junction, another class of bipolar switching,
is believed to be a result of the change of a ferroelectric’s
conduction band profile by the ferroelectric polarization
reversal [146–148, 216]. The alternation of carrier-depletion
width in ferroelectric PTO by ferroelectric switching is the first
model attempting to explain ferroelectric-resistive switching
[39]. Meyer and Kohlstedt assumed the existence of a gap at
the metal/ferroelectric interface, which separates the induced
charge on the metal from the surface charge on the ferroelectric
[216]. Namely, a high depolarization field was assumed in
their model. This interfacial gap is placed at one interface, i.e.
asymmetric interface. This asymmetry leads to polarization-
dependent profiles of the ferroelectric’s conduction band and
thus the polarization-dependent conductivity of delocalized
electrons in the ferroelectric.
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D S Jeong et al
An FTJ, another type of ferroelectric-resistive switch,
differs from the above-mentioned MFM junctions in its
mechanism for current transport through the ferroelectric,
which is quantum mechanical tunnelling [146, 147]. The
change of a ferroelectric’s conduction band profile with
respect to the polarization direction results in the alternation
of the tunnelling matrix element and thus the resistive
switching. However, resistive switching in some ferroelectrics
is not caused by the ferroelectric switching [217, 218].
One possible way to distinguish resistive switching from
ferroelectric switching is the simultaneous acquisition of
electric currents and ferroelectric-switching-related responses,
e.g. piezoelectric response, with respect to the applied voltage.
Kohlstedt et al have simultaneously obtained currents and
piezoelectric responses of PZT with voltage (see figure 18(a))
[217]. This figure clearly shows that the resistive and
ferroelectric switching behaviours are not coupled. More
precisely, the simultaneous switching of the ferroelectric
polarization and resistance at the same electric field would
be a precondition (but not sufficient) for ferroelectric-resistive
switching.
Resistive switching in such nominal ferroelectric-resistive
systems is perhaps attributed to a generic property of TMOs:
the inclusion of intrinsic defects. It is worth noting that
most perovskite-type TMOs (ABO3 ) are hypo-stoichiometric
compounds, and transition metal ions on ‘B’ sites can vary
their valence state [76, 219–221]. Therefore, the switching
perhaps falls into the VCM class. The same is true for some
nominal MR materials such as PCMO exhibiting the EPIR
effect [16, 151].
Nevertheless, ‘true’ ferroelectric-resistive switching has
been recently found in a BTO film on a blanket SRO electrode
[148]. This switching was measured by directly applying a
voltage to the BTO film surface through a CAFM tip. In this
study, the authors found bi-stable states (low and high direct
tunnelling currents) corresponding to ferroelectric up (+P) and
down (−P) polarization, respectively (see figure 18(b)). In the
same year, the same coupling was reported for a PZT thin film
grown on an LSMO electrode by Maksymovych et al [149].
By employing CAFM, they successfully measured the resistive
switching and piezoelectric response of the ferroelectric at the
same electric field, implying ferroelectric-resistive switching.
Ferroelectric-resistive switching seems to be hindered by TE
deposition in the FTJ junction fabrication. In the TE deposition
process, physical and/or chemical damage may be imposed on
the ferroelectric film, introducing CFs, so that ferroelectric-
resistive switching could not be achieved.
5. Are RRAMs memristors?
After Chua’s suggestion of the missing circuit element
‘memristor’ in 1971 [123], the concept had not attracted
great attention for more than three decades. In 2008,
Strukov et al at the Hewlett-Packard labs came out with
the idea that TiO2 -based resistive switches are examples of
the missing fourth circuit element [124]. This finding drew
considerable attention to many resistive switching systems that
have been widely referred to as ‘memristors’ or ‘memristive
Rep. Prog. Phys. 75 (2012) 076502 D S Jeong et al

Figure 18. (a) Simultaneous measurements of current and piezoelectric response of a MFM cell with a 6 nm thick PZT film. The
ferroelectric switching appears at about 170 kV cm−1 (0.5 V) and −170 kV cm−1 (−0.5 V) applied electric fields, while the resistive
switching can be observed at about 330 kV cm−1 (0.9 V) and −330 kV cm−1 (−0.9 V) applied electric fields. Reprinted with permission
from [217]. Copyright 2008, American Institute of Physics. (b) The same measurement on a 30 nm thick PZT film on a LSMO electrode.
This measurement was conducted using a CAFM tip. The curves show the correlation between the piezoelectric and current responses at a
tip bias of approximately −3.3 V, suggesting ferroelectric-resistive switching. Reprinted with permission from [149]. Copyright 2010,
American Association for the Advancement of Science.

systems.’ Considering the literal meaning of ‘memristors’,
i.e. ‘memory + resistors’, this terminology properly describes
resistive switching (memory switching) systems. However, if
this terminology is invoked with the original meaning that Chua
introduced, one should carefully judge whether ‘memristors’
correctly account for the resistive switching systems being
studied. The change in the memristance of a memristor
is caused by the cumulative number of charges q flowing
through the memristor. However, considering several bipolar
switching systems, for instance, VCM systems, the change in
the resistance results from electrochemical reactions, which are
given by functions of the applied ‘voltage’ rather than charge.
Memristance actually defines the relationship between
charge and magnetic flux [123]. In his comment on the paper
by Strukov et al, Mathur said that memristance corresponds
to the magnetoelectric coupling constant of a magnetoelectric
system (see [222] and references therein). The first finding of
the magnetoelectric effect dates back to the 19th century and
the history is very nicely overviewed in the review paper by
Fiebig [223].
6. Non-volatile memory application
With benefits of low power and high speed, RRAM is a
potential candidate for the next-generation NVM. Apart from
the viable parameters, e.g. on-to-off ratio, on-state current,
retention time and cycling endurance, main concerns for
the technological application are the scalability, stability and
switching speed. In the near future, RRAMs may become
universal memories that could replace FLASH memories,
DRAMs, and even hard disks, if the aforementioned concerns
are addressed.
Concerning the working principle of NVMs allows them
to be classified as either thermodynamic or kinetic memories.
Memories having the two binary values ‘0’ and ‘1’, defined by
energetically stable and distinctive states, are ‘thermodynamic
memories’. FRAMs and MRAMs belong to this category. +P
and −P in FRAMs are two stable states at zero electric field,
and the transition from one to the other can be achieved by
applying an electric field that differentiates the free energy of
one state from the other. In MRAMs, spin-up and down states
correspond to the binary values. They are also energetically
stable at zero magnetic field, and spin flip is done by applying
a magnetic field.
‘Kinetic memories’ have two different states: one in the
configuration of the ultimate minimum energy or a local
minimum (‘0’) and the other in the meta-stable configuration
with a higher energy (‘1’). Therefore, there is a difference
in energy between the two states even without an external
bias. The stability of these two states is a matter of the energy
barrier height (E10 ) for the transition from ‘1’ to ‘0’. The
reaction rate constant is likely given by ∼ exp(−(E10 /kT )),
where k and T denote the Boltzmann constant and temperature,
respectively. If E10 is sufficiently high, a written ‘1’ is able
to be retained for a sufficiently long time. FLASH memories,
PRAMs and RRAMs are regarded to belong to this ‘kinetic
memories’ category. The categorization is illustrated in
figure 19 with a schematic of a free energy versus configuration
diagram for each NVM.
In PRAMs, the amorphous phase corresponding to ‘1’
is less stable than the crystalline phase ‘0’. However, the
amorphous state can be retained for a sufficiently long time.
For RRAMs, a mechanism for the resistive switching is not
very well understood at this moment so that the categorization
of RRAMs is not very certain. Nevertheless, we conjecture
that the bi-stability of RRAMs is defined by kinetics rather
than thermodynamics from the configuration of CFs embedded
in the host insulating matrix, which is unlikely stable.
Regarding some experimental results of electroforming and
resistive switching features, e.g. the non-uniform distribution
of conductivity in a switching material, and Joule-heat-induced

25
Rep. Prog. Phys. 75 (2012) 076502
Figure 19. Definition of thermodynamic and kinetic NVMs and
some examples of each type. These energy versus configuration
diagrams illustrate the energetic stability of the binary values.
phase transition and non-stoichiometry, both LRS and HRS do
not appear to be thermodynamically stable under the operation
conditions, room temperature and an oxygen partial pressure
of approximately 0.2 atm.
6.1. Scalability of RRAMs
To be implemented in future technology, the scalability of
switching cells down to the nanoscale is an important criterion
for RRAM technology development. The configuration and
geometry of CFs in the host insulating matrix are most likely
critical factors in the scalability of RRAMs. When the
switching cells in an RRAM are scaled down below the cross-
sectional area of a single CF, the CF formation conditions are
perhaps very different from those in larger cells. Furthermore,
because Joule heat is believed to be involved in the switching
operation, the thermal crosstalk between neighbouring cells is
thought to be a critical scalability issue, which has been brought
up for PRAMs as well. At the moment, the development
of RRAMs is still in a beginning phase, namely, the current
status of RRAMs is still far from commercialization. More
scalability issues would be brought up as knowledge on the
working principle of RRAMs becomes deeper. To current
knowledge on the working principle, it is difficult to diagnose
all the potential issues related to the scalability of RRAMs.
Therefore, more vigorous investigations on the mechanism
need to be conducted for a better understanding.
In addition to a conventional active RRAM structure
of 1T1R configuration, a crossbar-array architecture built
using passive switching elements has been positively regarded
as an RRAM architecture for ultra-large-scale integration
[224, 225]. Since no MOSFETs are used in the crossbar-array
domain of a crossbar-array-based RRAM, this architecture is
able to achieve the 4F 2 design rule. Furthermore, by stacking
n crossbar-array layers, one can scale it further down to 4F 2 /n.
Scaling down results in an increase in the resistance
of the bit- and word-lines, becoming critical issues in this
architecture. A significant voltage drop along the down-scaled
lines in the crossbar-array hinders operational uniformity in the
array. During electroforming, writing, erasing and reading, a
26
D S Jeong et al
voltage applied to each cell in the array will be different so that
miswriting and misreading easily take place unless the writing
and erasing voltage margins and marginal differences in the
resistance between HRS and LRS are large enough.
Considering that many switching cells share one line, e.g.
M cells in an M × N array, the binary value written in each
cell can be misread. The worst case occurs when one reads an
HRS cell in the array where all the other cells are in the LRS. In
this case, the measured read current is attributed to the current
flowing through not the HRS cell but the neighbouring LRS
cells, which is called ‘sneak current’. Therefore, the bit stored
in the HRS cell cannot be correctly read. To solve this problem,
cell-selection devices are necessary in the passive crossbar
array. P–n junction diodes [226] (asymmetric MIM diodes),
e.g. Pt/TiO2 /Ti [227, 228], ovonic threshold switches [30], and
Zener or soft breakdown diodes are possible candidates for
cell-selection devices.
With increasing integration density of passive crossbar-
array-based RRAMs, high rectification ratios of the cell-
selection devices are desperately necessary, implying that the
proper specification of cell-selection devices becomes very
critical. In unipolar-switching-based crossbar arrays, any cell-
selection devices among the aforementioned candidates are
available due to the independence of the unipolar switching
operation from the voltage polarity, whereas for bipolar-
switching-based arrays, only ovonic threshold switches and
Zener diodes are available. Utilizing bipolar switching
elements in crossbar arrays will bring about more restrictions.
In addition to the application of cell-selection devices, Linn
et al demonstrated ‘complementary resistive switches’ that can
be solely employed in crossbar arrays without cell-selection
devices [229]. Two complementary memory switches facing
each other make the array quite free from misreading [229].
As discussed earlier, uniform electroforming of switching
cells in a crossbar array becomes more difficult with further
scaling down because voltage drops along the lines hinder
application of the same electroforming voltage to each cell.
The ultimate solution of this problem may be to achieve
electroforming-free resistive switching cells. A resistive
tunnel junction (RTJ) with a thin oxide tunnel barrier
(native AlOx ) and an oxygen-reactive electrode (Ti) has been
recently demonstrated as an electroforming-free cell exhibiting
excellent uniformity of bipolar switching behaviour [167].
6.2. Stability of RRAMs
The lifetime of CFs formed in an insulating matrix would be a
key parameter determining the stability of switching cells in an
RRAM. As both LRS and HRS of the switching cells are not
thought to be energetically stable, under severe stationary or
alternating stimulation the switching cells may lose their state
stability, leading to serious retention or endurance problems.
Moreover, gas evolution and Joule heat, anticipated during
electroforming and resistive switching, are likely to be serious
obstacles that hinder achieving highly stable RRAMs.
These problems may be solved by choosing proper
switching and electrode materials. For instance, Ta/TaOx /Pt
switching cells with disc-shaped TEs have been recently found
Rep. Prog. Phys. 75 (2012) 076502
to endure more than 1010 operation cycles [49]. Although
many different switching materials share more or less common
working principles, each material should have a different
degree of operational stability. The detailed understanding
of switching mechanisms is perhaps able to suggest guidelines
for a choice of switching and electrode materials as well as
switching cell design. By means of this understanding, the
high stability of RRAMs can be achieved.
6.3. Switching speed of RRAMs
RRAMs as universal memories should catch up with DRAMs
in terms of switching speed (DRAM write/erase time;
<10 ns/<10 ns). Switching speed measurement has been
intensively conducted on the prototypical resistive switching
material TiO2 [48, 230–232]. The results have demonstrated
very fast switching speed of TiO2 -based switching cells, which
is now comparable to or even faster than the operation speed
of DRAMs. Hermes et al successfully measured both set
and reset switching of Pt/Ti/TiO2 /Pt cross-point junctions
using voltage pulses of 2 ns rise-, 1 ns plateau- and 2 ns
fall-time [48]. The voltage pulses that they applied for
the measurement and the corresponding current responses
are clearly seen in [48]. Note that caution should be used
in switching speed measurements, especially since applied
voltage/current pulses are very short. Due to several effects
mainly caused by impedance mismatch, e.g. the ringing effect
[233], programmed voltage/current pulses in fact differ from
their actual shapes. The shorter the programmed pulse width,
the more obvious is such a pulse distortion. Therefore,
it is of importance to monitor the shape of applied pulses
simultaneously.
Pt/Ti/TiO2 /Pt junctions have been found to exhibit multi-
level switching behaviour depending on the width of applied
voltage pulses [232]. Kügeler et al have examined voltage-
pulse-driven switching in Pt/Ti/TiO2 /Pt junctions with two
different pulse widths, 10 and 50 ns, and observed different
LRSs relying on the pulse width [232].
7. Concluding remarks and outlook
We reviewed the technological status of RRAMs as emerging
NVMs, some basics of resistive switching phenomena,
candidate materials and mechanisms for electroforming and
resistive switching with particular emphasis on binary TMOs.
There are many more switching materials and mechanisms
that are not covered by this review. The first reason
for the variety of the mechanisms is that our current
understanding of these scientifically and technologically
important phenomena is not quite clear. The second reason
is the lack of consistent experimental data reported in different
publications. The result is various switching mechanisms
for even the same switching materials. This may be due to
different electroforming procedures or the stochastic nature
of electroforming itself. As the initialization process of
resistive switching measurement, electroforming strongly
affects the resulting resistive switching behaviour. In spite
of the importance of this initialization step, it seems that
27
D S Jeong et al
electroforming is not seriously taken into consideration in
many publications. Indeed, when one surveys papers on
resistive switching, one can often find that the quantitative
explanation of the electroforming procedures is missing.
Therefore, to better our understanding, emphasis on systematic
electroforming studies is necessary.
From a technological point of view, this complicated
initialization procedure should be avoided: electroforming-free
RRAMs are preferable. Recent progress in electroforming-
free RRAMs was demonstrated in RTJs by Jeong et al
[167]. The RTJs showed great uniformity of bipolar switching
behaviour and no obvious structural change during the
switching operation.
Considering other dielectric- or ferroelectric-related or
hybrid-type emerging memories, the observation of room
temperature electronic conductivity at ferroelectric domain
walls in insulating multiferroic BFO opens the door for logic
and memory applications [234, 235]. The extremely small
size of such domains and the possibility of control with
applied electric fields are of great interest in realizing high-
density memories. However, device applications of such
conducting nanoscale features are in their infancy and hence
have to be investigated in detail. At present, there are
four contenders for the next generation of RAMs based on
dielectrics: magnetoelectric RAMs [236], RRAMs, MottFETs
[237] and domain-wall RAMs [238]. The most recent
breakthrough in RRAMs is the demonstration by Jiang et al
that such switching materials need not be highly insulating,
and that true ferroelectric-resistive RAMs can be based not on
CFs but on homogeneous SBH over the entire pad area [156].
The work by Jiang et al gives reversible switched currents of
>1000× that of the early devices of Blom et al (which were
a few mA cm−2 ). Magnetoelectric RAM was first proposed
by Bibes et al in 2008 as a development of magnetic tunnel
junctions [236]. More recently Hu et al have shown how to
make magnetoelectric NOR, NAND and NOT gates in addition
to memories [239]. These gate designs may have a large
commercial impact on some niche markets. MottFET is a kind
of metal-gate FET in which the gate material can be driven
to a metal-to-insulator phase transition via an applied electric
field. The favoured materials are nickelates, on which Catalan
has a recent review [237]. Finally, the use of ferroelectric
nano-domain walls, which can be highly conducting [234]
and ferromagnetic when surrounded by non-ferromagnetic
domains [240], has been recently discussed for nanoelectronics
in a review paper [238].
Acknowledgments
DSJ would like to acknowledge research grants from the Korea
Institute of Science and Technology (grant nos 2V02410 and
2E22123). The authors thank Professor Rainer Waser for
fruitful comments.
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