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Coexistence of bipolar and threshold resistive switching in TiO2 based structure with

embedded hafnium nanoparticles

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2017 J. Phys. D: Appl. Phys. 50 045103

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 Journal of Physics D: Applied Physics

J. Phys. D: Appl. Phys. 50 (2017) 045103 (10pp) doi:10.1088/1361-6463/aa5161

Coexistence of bipolar and threshold

resistive switching in TiO2 based structure
with embedded hafnium nanoparticles
Irini Michelakaki1,3, Panagiotis Bousoulas1, Spyros Stathopoulos1,
Nikos Boukos2 and Dimitris Tsoukalas1
1
  Department of Applied Physics, National Technical University of Athens, 15780 Zografou, Greece
2
  Institute of Nanoscience and Nanotechnology, National Centre for Scientific Research ‘Demokritos’,
15310 Aghia Paraskevi, Greece

E-mail: michelakaki.irini@gmail.com

Received 14 September 2016, revised 20 November 2016

Accepted for publication 2 December 2016
Published 29 December 2016

Abstract
The coexistence of nonvolatile memory switching and volatile threshold switching in a
single device is of importance for suppressing the sneak-path currents in crossbar resistive
memory architectures. This study demonstrates that the combination of a thin film of TiO2
with hafnium nanoparticles in Au/Ti/TiO2/Hf nanoparticles/Au device configuration enables
conversion between memory switching and volatile threshold switching by adjusting the
current compliance through the materials stack. The presence of hexagonal closed packed
Hf nanoparticles, a synthesis of which has not been reported before, is critical for the
device operation that exhibits beneficial features as it is forming free and operates at low
voltage and power consumption. Analysis of measured current–voltage (I–V) characteristics
reveal a filamentary nature of switching phenomena and present operating similarities with
electrochemical metallization cells suggesting that Hf metal atoms and not only oxygen
vacancies are responsible for conductive filament formation.

Keywords: nanoparticles, titanium dioxide, resistive memory, hafnium, memory switching,

threshold switching

(Some figures may appear in colour only in the online journal)

1. Introduction and volatile threshold switching (TS) [4–8]. When MS and TS

Resistance random access memories (RRAM) are promising
candidates for the next generation nonvolatile memory tech-
nology. An important class of memristive devices are oxide
based resistive switches, which consist of a simple metal/
oxide/metal (MIM) thin-film stack [1, 2]. Because of their
simple structure, cross-point architecture with high density
of memory cells has been proposed. Nonetheless, an impor-
tant issue in the cross-point structure is the interference from
sneak-path currents through neighboring cells [3]. Among
others, a solution to this problem is the use of a resistive ele-
ment which combines in one device non-volatile memory (MS)
3
Author to whom any correspondence should be addressed.
mode are combined in a single device, the former can be used
for nonvolatile information storage while the latter will serve
as a selector [9–11]. A memory switching device can retain
low resistance state (LRS) and high resistance state (HRS)
after the external voltage has been removed. On the other hand
in a threshold switching device the conducting LRS is retained
as long as an appropriate value of voltage is applied, otherwise
the device resets to the insulating HRS, this feature being what
makes it useful as a selector device to suppress the sneak path
problem. Low power consumption and low voltage operation
is another critical requirement for an emerging electron device
concept either this can be used as a memory or logic element.
Beyond the apparent application of metal oxide based devices
as memory elements as discussed above it is noteworthy to

1361-6463/17/045103+10$33.00 1 © 2016 IOP Publishing Ltd  Printed in the UK

J. Phys. D: Appl. Phys. 50 (2017) 045103
Figure 1.  (a) Schematic illustration of the Au/Ti/TiO2/Hf nanoparticles/Au containing sample. (b) Top view scanning electron microscopy
(SEM) image of the active layer (TiO2 and Hf NPs) on Si substrate. The textured TiO2 surface is due to the underlying Hf nanoparticles.
(c) For reasons of comparison a top view SEM of TiO2 thin film on Si without underlying Hf nanoparticles is added.
mention that particularly TS or metal insulator transition based
devices connected in series with the drain of a metal-oxide-
semiconductor field-effect-transistor have been recently
proposed as a potential solution to obtain steep slope charac-
teristics [12, 13]. This approach could enable overcoming the
60 mV/dec subthreshold swing theoretical limit that is critical
for transistor static power dissipation.
In this paper we show the conversion between nonvolatile
memory switching and threshold switching by appropriately
adjusting the current compliance, at room temperature, within
a single device that incorporates hafnium nanoparticles (NPs)
within a metal oxide in the following MIM stack configuration:
Au/Ti/TiO2/Hf NPs/Au. Our results show that Hf NPs have a
critical role in the device operation. We remark that although
the fabrication of hafnium oxide NPs has been already reported
using chemical synthesis with potential medical applications
[14, 15] we have not identified any prior study demonstrating
the growth of hafnium NPs but only computational invest­
igations [16]. The device shows a room temperature forming
free operation at low voltage and with low power consumption.
Furthermore during volatile operation it exhibits good char-
acteristics as a selector [10], such as a high selectivity ratio
about ~105 (ON/OFF ratio) and steep turn on voltage 0.25
mV/dec. The current–voltage characteristics for both modes
of operation indicate a similar switching mechanism between
bipolar and threshold switching which is based on filamen-
tary switching. Although oxygen vacancies are considered
as the major mobile species driving to resistive switching in
TiO2 [17] the extremely steep slope cur­rent–voltage response
observed in the proposed device, very similar with electro-
chemical metallization cells, suggests that incorporation of Hf
metal atoms in the filament formation, originating from NPs
surface, appears also a likely physical interpretation of the
measurements. The study is supported by microscopy imaging
and structural investigations using x-ray diffraction.
2.  Device fabrication and material characterization
Figure 1 shows a schematic illustration of the device struc-
ture. The device fabrication process was based on physical
vapor deposition method (PVD) and it is described below.
2
I Michelakaki et al
First the bottom electrode was deposited by e-gun evapora-
tion of a 4 nm Ti adhesion layer followed by a 40 nm Au layer
on a SiO2 substrate. Then metallic Hf NPs produced by an
inert gas condensation method were soft landed on the Au sur-
face. Deposition of a 20 nm RF sputtered thin film followed.
Finally the top electrode was formed, by e-gun evaporation of
a 4 nm Ti and 40 nm Au layer, which were patterned by lift-off
lithography.
The Hf NPs and TiO2 fabrication were performed consecu-
tively in the same vacuum chamber without vacuum breaking.
For Hf NPs fabrication, a vapor of Hf atoms metal was pro-
duced by dc sputtering of a high purity Hf target (99.9%) in a
high pressure Ar atmosphere, at room temperature. The high
pressure led to aggregation of the Hf atoms into particles,
which were forced due to a pressure difference to enter a dep-
osition chamber, where they soft landed on the Au substrate.
Transmission electron microscopy (TEM) and atomic
force microscopy (AFM) images revealed that the NPs have
hexagonal shape, with size of 7 nm  ×  12 nm (height  ×  diam-
eter) and surface density about 2 * 1011 cm−2 (figure 2(a)).
Their diameter size and its distribution were measured from
the TEM images while their height was estimated from AFM
images. Isolated NPs of large diameter (~30 nm) were also
observed. TiO2 deposition was carried out at room temper­
ature using a high purity (99.9%) metallic Ti target in the
presence of oxygen reactive gas. The chamber pressure prior
to deposition was 1.2 * 10−6 mbar, the sputtering power 200
W, and the argon and oxygen flow was 10 sccm and 2.5 sccm
respectively.
Structural characterization of the TiO2 film and the Hf
NPs was performed by grazing incidence x-ray diffraction
(GIXRD). An X’PERT Pro diffractometer was employed for
x-ray measurements. The instrument was operated in a con-
tinuous scan mode in increments of 0.05° 2θ, and counts were
accumulated for 10 s at each step. The angle of incidence ω
was set to 0.5°. The x-ray patterns are illustrated on figure 3.
Concerning the hafnium NPs the x-ray patterns reveal that
they have hexagonal closed packed structure (HCP) (figure 3).
The HCP structure detected agrees with previous thermody-
namic calculations presenting the phase diagram of Hf NPs
with the variation of particle size and temperature [16] since
J. Phys. D: Appl. Phys. 50 (2017) 045103 I Michelakaki et al

Figure 2.  (a) Transmission electron microscopy (TEM) image of the as deposited Hf nanoparticles. The nanoparticles have hexagonal
shape and size 7 nm  ×  12 nm (height  ×  diameter). The density of the nanoparticles illustrated on the TEM image is equal to 2 * 1011 cm−2.
The inset shows a histogram with the diameter distribution. (b) High resolution transmission electron microscopy (HRTEM) image, of a
hafnium nanoparticle that appears to have a core-shell structure: in the inner core area lattice fringes of d  =  0.275 nm corresponding to
(1 0 0) Hf can be seen marked as A. The outer shell is composed of orthorhombic HfO2 nanocrystallites indicated by arrows and exhibiting
(0 0 2) of d  =  0.324 nm and (1 0 1) of d  =  0.295 nm lattice fringes embedded in an amorphous layer. Finally Moirre fringes originating from
double diffraction of another nanoparticle marked as B superimposed on the main one can be seen.

during the used gas condensation technique for NP growth
temperature remains relatively low [18]. The x-ray pattern
reveals that two other peaks at 30.76, 50.45° which fit with
orthorhombic HfO2 are present. The most likely explana-
tion is that the outer shell of the NPs is oxidized due to the
naturally occurring reaction of hafnium with oxygen when
exposed to atmospheric air. This observation is confirmed by
high resolution transmission electron microscopy (HRTEM)
imaging, where the NPs appear to have a core-shell structure
(figure  2(b)). The lattice fringes in the inner core area cor-
respond to (1 0 0) hexagonal hafnium and the outer shell is
composed of orthorhombic HfO2 nanocrystallites.
To verify the oxidation of the NPs, oxidation studies were
performed at low temperatures (Tox  =  150 °C and 300 °C)
under oxygen flow for 1 h that demonstrate that Hf NPs oxi-
dize easily at low temperatures. X-ray patterns reveal that
already at T  =  150 °C partial oxidation of the Hf NPs to
HfO2 occurs because the HfO2 peak at 30.76° (figure 3(a))
is enhanced and at T  =  300 °C complete transformation of
the Hf NPs to HfO2 occurs (figure 3(a)). Concerning the TiO2
structure the x-ray pattern reveals that is has an amorphous
structure (figure 3(b)).
3.  Electrical characterization
To investigate the resistive switching behavior of the device
electrical measurements were performed using HP4140
picoamperometer. In all measurements the voltage was
applied to the top Au/Ti electrode and the bottom Au electrode
was grounded. Furthermore it has to be pointed that none of
the devices required any electroforming step for the resistive
switching operation. Finally all measurements were performed
on electrode pads with lateral dimensions 100 µm  ×  100 µm.
For reasons of comparison the characteristic I–V of a
device without Hf NPs (Au/(4 nm Ti)/(20 nm TiO2)/Au) was
recorded, and as shown in figure 4 it exhibits rectifying char-
acteristics. When Hf NPs were introduced the characteristic
I–V curve changed completely. The main feature of the Hf
NPs containing device is that the volatility can be tuned by
adjusting the current compliance (CC) (figures 5 and 6). We
observed bipolar memory switching when CC was down to
10−7 A under DC voltage sweeps (figure 5). When a negative
voltage sweep from 0 to  −1.5 V was applied, a sudden current
increase was observed at a voltage Vset  ≈  −0.8, and the device
was set from HRS to LRS. The device remained at LRS and
reset to HRS when a positive voltage of about Vreset  ≈  +0.5
R
V was applied. The resistance ratio was equal to Roff = 103 at
on
V  =  −0.1 V.
When CC was increased to 10−5 A threshold switching
was obtained as shown in figure 6. The device switched from
HRS to LRS at Vth  ≈  −0.8 V. When the voltage was swept
reversely the current followed the compliance current, until it
dropped suddenly at hold voltage Vhold  ≈  −0.3 V, at this point
the device was switched back to HRS. It should be noted that
the threshold voltage Vth and set voltage Vset are equal, indi-
cating a similar mechanism between bipolar and threshold
switching. Small variation between these values was in the
Roff
range of 0.1 V. The resistance ratio was equal to Ron
≈ 10 5 at

3
J. Phys. D: Appl. Phys. 50 (2017) 045103 I Michelakaki et al

Figure 3.  X-ray pattern of (a) nanocrystalline hafnium nanoparticles with HCP structure at room temperature (black line) and after
oxidizing at T  =  150 °C (red line) and at T  =  300 °C (blue line) under oxygen flow for 1 h (b) amorphous TiO2 thin film. All x-ray patterns
were recorded with GIXRD method.

Figure 4.  Rectifying current voltage I–V curve of a Au/4 nm Ti/20 nm TiO2/Au device. No difference is observed when (a) no current
compliance is applied and (b) IC  =  10−7 A is applied.

Figure 5. Characteristic I–V curve of the device operated at bipolar memory switching mode when the current compliance was adjusted
equal to (a) IC  =  10−8 A and (b) IC  =  10−7 A.

4
J. Phys. D: Appl. Phys. 50 (2017) 045103 I Michelakaki et al

Figure 6.  Current voltage I–V curve of the device operated at threshold switching mode when current compliance was adjusted to
(a) 10−5 A and (b) 10−4 A.

reading voltage between Vth and Vhold. Furthermore the device

exhibited steep turn-on slope about 20 mV/dec. In order to test
the sharpness of the turn-on slope we decreased the voltage
step to 1 mV, and observed an abrupt current jump from 10−9 A
to 10−5 A (4 decades) for 1 mV step (inset figure 6(a)) which
leads to a very sharp turn-on slope about 0.25 mV/dec. The
features of high ON/OFF ratio in combination with sharp
voltage slope suggest that the present device might be an
interesting candidate for future threshold selector application
in crossbar array architectures [10].
Finally it is worth noticing that when IC  =  10−4A (figure 6(b))
the current could not follow the current compliance value and
dropped directly.
In figures 5 and 6 the I–V curves exhibit non zero crossing
characteristics which might be attributed to a nanobattery
effect. Chemical processes in nanoionic ReRAM cells result
Figure 7. Current–voltage curve of the device without applying any
in an electromotive force, which suggests the presence of a current compliance. The abrupt current jump disappears.
nanobattery inside the memristive device as an inherent prop-
erty of the system [19]. compliances 10−7 A and 10−5 A respectively. In the case of
When the device was operated with current compli- IC  =  10−7 A (figure 8(b)) and during the first pulse applica-
ance between 10−7 A  <  IC  <  10−5 A both switching modes tion, an abrupt current jump to the CC value was observed for
appeared randomly. V ~  −0.85 V. The current sustained the CC value and at the
When no current compliance was applied, the abrupt cur­rent same time the voltage dropped. During the second pulse appli-
jump disappeared and the characteristic I–V curve (figure 7) cation (Vp  =  −0.05 V) the current retained its value although
appeared similar to the I–V of an Au/Ti/TiO2/Au stack without a time interval where no bias was applied preceded. This con-
NPs, where the electrical hysteresis was attributed to move- firms the nonvolatile character of the device when IC  =  10−7
ment of oxygen vacancies [20, 21]. A. In the case of IC  =  10−5 A (figure 8(c)) the same proce-
In order to test the volatility of the device, operation with dure was followed. During the first pulse application, at about
voltage pulses was performed. A voltage pulse of Vp  =  −1 V V ~  −0.85 V the current jumped suddenly to 10−5 A, but it
(pulse 1) was applied to switch the device to LRS and at the could not be retained there and dropped. During the applica-
same time the responding current was recorded. After the SET tion of pulse 1 the voltage fluctuated in order to sustain the cur­
pulse application, no voltage was applied for a short time rent compliance value. When the reading pulse (Vp  =  −0.05
interval and then a second pulse (pulse 2) of Vp  =  −0.05 V V) was applied the current was low as expected. This behavior
followed. The shape of the two pulses is illustrated at confirms the volatile character of the device. It appears that
figure  8(a). This measurement was performed for current the conductive path which is formed during the set operation
5
J. Phys. D: Appl. Phys. 50 (2017) 045103
Figure 8.  (a) Shape of the pulses applied for setting the device to the LRS (pulse 1) and reading pulse (pulse 2). Both pulses have identical
trapezoidal shape, with different amplitude (shown not in scale). (b) and (c) The responding current of the stimulating pulse of current
compliance equal to (b) IC  =  10−7 A (c) IC  =  10−5 A. Where V is the measured voltage applied. The fluctuation of V is due to the current
compliance.
is unstable and dissolves when no voltage is applied or when
voltage drops below Vhold.
Furthermore I–V cycles of the device operating at non-
volatile mode (IC  =  10−8 A) are shown in figure 9(a). There
are 30 set/reset switching cycles shown in this figure  and
typical bipolar switching was confirmed in all cycles. The
resistances were evaluated at V  =  −0.25 V for the forward
and backward voltage sweep. The endurance properties are
summarized in figure 9(b).
Finally retention measurements were performed by
applying a negative pulse of Vp  =  −1 V, tp  =  1 ms by set-
ting at the same time the current compliance at IC  =  10−8
A. The HRS state was set with a voltage pulse of Vp  =  1 V,
tp  =  1 ms by setting at the same time the current compliance
at IC  =  10−8 A to break the filament. The current reading
was performed at a voltage of  −0.25 V. The measurements
have been performed at room temperature and the results are
shown in figure 10. They reveal that LRS remains stable for
about 2000 s, and afterwards a gradual decrease of the current
is observed and the device returns to the HRS which is not
modified in that time period. We remark that we have meas-
ured a 10% of devices exhibiting stable LRS for more than
105 s but these are not representative of the average retention
performance.
4. Discussion
TiO2 is known as an n-type semiconductor since oxygen
vacancies behave as n-type dopants [22]. Ti/TiO2 interface is
considered as an ohmic contact because Ti chemically reduces
6
I Michelakaki et al
TiO2 to TiO2−x, creating a significant concentration of oxygen
vacancies, which results in the reduction of the electronic
energy barrier at the Ti–TiO2 interface [23]. On the other hand,
due to the apparent interaction of Hf with the surrounding O2,
as evidenced by the oxidation experiments presented in sec-
tion 2, it is assumed that Hf NPs create significant concentra-
tion of oxygen vacancies V 2+O in the TiO2 bulk, leading to the
formation of substoichiometric TiO2−x and HfO2−x in the area
around the NPs. Concerning the Au/TiO2 interface it forms a
Schottky contact as in that case Au is chemically inert and it
does not induce oxygen vacancies at the TiO2 interface [23].
Relying on the above arguments a schematic illustration of
the oxygen vacancies distribution inside the TiO2 matrix is
represented on figure 11(a).
In line with the above, the device without NPs showed
rectifying characteristics due to the TiO2/Au Schottky bottom
interface (figure 4(a)). When negative voltage is applied the
diode is forward biased and the current increases, and when
positive voltage is applied the junction is reversely biased and
current flow is reduced. This result is in fully accordance with
other group results [24, 25]. Furthermore, the I–V character-
istic of the device without NPs did not depend on the cur­
rent compliance value level (figure 4(b)). Due to the above,
we conclude that the conversion from non-volatile to volatile
switching and the I–V characteristic of the NPs containing
device is triggered by the Hf NPs.
As far as it concerns the device with Hf NPs and in order
to clarify the prevailing conduction mechanism fittings with
various conduction models were performed. At LRS and
for memory switching mode (IC  =  10−7 A, figure 12(a)) the
J. Phys. D: Appl. Phys. 50 (2017) 045103
Figure 9. (a) I–V cycles of the device when current compliance
was set equal to IC  =  10−8 A. (b) Endurance of the device evaluated
at  −0.25 V from (a).
linearity curve with slope equal to ~1 indicates an ohmic con-
duction behavior. At HRS for positive voltage, in both cases of
memory switching (IC  =  10−7 A, figure 12(b)) and threshold
switching (IC  =  10−5 A, figure 12(c)), the experimental data
are well fitted using either Poole–Frenkel (P–F) conduction
model or trap assisted tunneling (TAT) mechanism [26].
In case of P–F model the extracted dielectric constant εr ~ 1.6
is unreasonably small for TiO2. Consequently, TAT was
accepted as the most likely conduction mechanism at HRS for
V  >  0. From the fitting parameters the trap energy level was
calculated as Φt  ≈  0.16 eV and Φt  ≈  0.13 eV for the memory
switching and threshold switching mode respectively. These
values are close to those reported in the literature for oxygen
vacancy traps in TiO2 [27].
The similarities in current–voltage curves between the
bipolar and threshold switching operation suggest that both
operation modes are governed by the same mechanism. The
ohmic behavior at LRS demonstrates the formation of a con-
fined conducting filament during the set process. Interfacial
resistive switching based on modulation of a Schottky barrier
by movement of ionic species, cannot be responsible for the
observed resistive switching, because it is inconsistent with
the measured linear LRS I–V characteristic and the observed
7
I Michelakaki et al
Figure 10.  Retention measurements, by applying pulses  −1 V and
1 V and duration tp  =  1 ms (read voltage  −0.25 V). The current
compliance was IC  =  10−8 A.
abrupt transition from HRS to LRS [24]. We then propose that
the filament is composed of Hf atoms and oxygen vacancies,
and that both valence change mechanism (VCM) and electro-
chemical metallization mechanism (ECM) should be involved
in the resistive switching.
The following mechanisms are then proposed to support
this argument. When a negative voltage is applied, oxygen
vacancies V 2+ O drift from the bottom electrode towards
the cathode. Simultaneously due the presence of the hex-
agonal shape Hf NPs the electric field is locally enhanced.
Loosely bound Hf surface atoms get oxidized to Hf+4 cations
(Hf  →  Ηf+4  +  4e−) which migrate through the solid TiO2
electrolyte, towards the cathode where they are reduced by
the electrons flowing from the cathode (Ηf+4  +  4e−  →  Hf).
The precipitations of Hf metal atoms at the cathode lead to
a growth of the metal protrusion, which finally reaches the
anode to form a highly conductive filament, and switches the
device to LRS at V  =  −0.8 V (figure 11(b)). We expect that
loosely bound Hf atoms generation is related with NP surface
oxidation effect taking place in the oxygen rich environment
during TiO2 deposition as observed for the as deposited NPs
oxidized in air at room temperature (figure 2(b)). The above
description is in line with current understanding about the
operation of an ECM memory [28, 29]. This process leads to
the formation of a filament composed by V 2+ O and Hf atoms.
Although transition metal oxides operate as valence change
memories, where resistive switching is driven by oxygen
vacancies [17, 20], recent publications demonstrated that also
Ta, Ti, Hf transition metal cations are involved in the conduc-
tive filament formation and the devices can show both VCM-
and ECM-type memristive switching [30–32]. Furthermore
Ag cation movement and Ag nanofilament formation in TiO2
has been reported in Ag/TiO2/Pt structures [33].
Although we cannot bring direct evidence that Hf atoms
are involved in the filament formation, our RRAM device
shows I–V characteristic similar to those of an electrochem-
ical metallization cell. The high ON/OFF ratio together with
the abrupt current jump observed at low voltage, the linear I–V
at LRS, the convertible resistive switching between bipolar
J. Phys. D: Appl. Phys. 50 (2017) 045103 I Michelakaki et al

Figure 11.  (a) Schematic illustration of oxygen vacancies distribution when no bias is applied. (b) Schematic illustration of ions movement
when negative voltage is applied. The formation of a filament composed of Hf atoms and oxygen vacancies results to the resistive switching
of the device to the conducting LRS. (c) Schematic illustration of ions movement when positive voltage is applied. Filament dissolution is
observed due the drift back towards the bottom electrode and thermal diffusion of ionic species.

Figure 12.  (a) Fitting with ohmic mechanism the LRS of the device at memory switching mode when IC  =  10−7 A. (b) and (c) Fitting with
TAT mechanism the HRS for positive voltage of the device operating at (b) memory mode IC  =  10−7 A and (c) threshold switching mode
IC  =  10−5 A.

and threshold switching are features usually observed at elec-
trochemical metallization based systems in which the filament
consists of metal atoms [28, 34–37]. Furthermore, if the device
was a conventional VCM memory, the set and reset process
should have contrary polarity to those observed as the oxygen
deficient region normally lies at the top electrode due to the Ti
metallization [20, 24]. Considering a cylindrical shape of the
filament, its diameter was calculated from equation (1):
4L
RLRS = ρfil 2
(1)
πD
where RLRH is resistance of the device at LRS (RLRH  =  550 kΩ
is calculated from the intercept of lnJ–lnE curve, figure 12(a)),
L is the filament length (thickness of TiO2 approximately
20 nm), ρfil is the resistivity of the filament (ρHf ~ 331 nΩ m,
ρVo ~ 10−4 Ω m [38]) and D the filament diameter.
Considering that the filament consists only of Hf atoms the
filament diameter equals ~0.15 nm, while considering that it
consists only of oxygen vacancies its diameter equals ~2 nm.
These values of filament diameters are generally consistent
with those reported in the literature [33, 39]. The size of the
filament is an important parameter for estimating the ultimate
packing density of the RRAM device. Small filament size sug-
gests that the memory cell size can in principle be scaled down
to less than ten nanometers. This is beneficial for high density
memory applications. On the other hand a thin switching fila-
ment may have an impact on the structural instability which
results in a poor retention property, most notably for the low
resistance state (figure 10) [33].
In the following we discuss the mechanisms in the reset
state for both modes of operation. In the bipolar switching
mode the device resets by applying a positive voltage. During
the reset process the CF dissolves due to the drift back of V 2+
O
and Hf cations towards the bottom electrode (figure 11(c)).
Furthermore the dependence of the I–V characteristic on cur­
rent compliance is direct evidence that the filament dissolu-
tion is also enhanced by Joule heating phenomena [5].
In the threshold switching mode the device resets by
applying a higher CC value and negative voltage. The cur­
rent increase through the filament during the SET process
(higher CC) is accompanied by elevated temperature due to
Joule heating. The high temperature accelerates the thermal
diffusion of the oxygen vacancies and Hf atoms out of the
filament and results in the filament rupture and dissolution.

8
J. Phys. D: Appl. Phys. 50 (2017) 045103
This observation is in accordance with other research group
data reporting transition from bipolar to threshold switching
by increasing CC value [4, 5, 40].
Furthermore the fact that no current jump for negative
voltage is observed when no current compliance is applied
(figure 8), it is further evidence of the above interpretation of
the switching mechanism. We believe that in the case of no
current compliance, although not observed in the I–V charac-
teristic, a filament might be formed, but due to the high cur­
rent flow it dissolves rapidly. We anticipate that in this case the
response time of the current compliance might be longer than
the time for the filament formation and dissolution, and thus
filament formation cannot be recorded. Finally during positive
voltage sweeping from 2 V to 0 V, the conduction mechanism
is attributed to TAT in both cases i.e. bipolar and threshold
switching. When positive voltage is applied V 2+ O drift under
the electric field towards the bottom electrode. This move-
ment induces a high density of traps (oxygen vacancies) in the
TiO2 bulk, and allows electron transfer through TAT mech­
anism [20, 41].
5. Conclusions
In this work we have demonstrated the conversion between
nonvolatile memory switching and threshold switching, within
a single hybrid MIM device with Au/Ti/TiO2/Hf NPs/Au struc-
ture, by adjusting the current compliance. Growth of hafnium
NPs is demonstrated for the first time in the literature and
their critical role on the device operation clearly illustrated.
The device operates as nonvolatile bipolar resistive switching
memory when the current compliance is lower than 10−7 A,
but when the current compliance increases in the range from
10−5 A to 10−4 A the device operates as volatile threshold
switching memory. Interpretation of the data by fitting with
appropriate conduction mechanisms reveals that the switching
mechanism is due to the formation of nanoscale dimension
filament. Striking similarities of the I–V characteristics with
electrochemical metallization cell suggest that except of
oxygen vacancies present in the metal oxide layer, Hf atoms
originating from the NPs are likely to participate in the fila-
ment formation. The nanoscale filament dimensions are bene-
ficial for high memory density application. It is worth noticing
that the device is forming free, exhibiting low voltage and low
power operation features. Furthermore during volatile opera-
tion it shows remarkable characteristics as a selector, such as
a high selectivity ratio about ~105 (ON/OFF ratio) and steep
turn on voltage 0.25 mV/dec with these properties being also
of interest for steep slope logic devices like the ones proposed
recently [12, 13].
Acknowledgment
The authors would like to acknowledge financial support from
research program ‘Aristeia II’ (Grant No. 4543). This research
has been co-financed by the European Union (European Social
9
I Michelakaki et al
Fund ESF) and Greek national funds through the Operational
Program ‘Education and Lifelong Learning’ of the National
Strategic Reference Framework (NSRF).
References
[1] Jeong D S, Thomas R, Katiyar R S, Scott J F, Kohlstedt H,
Petraru A and Hwang C S 2012 Emerging memories:
resistive switching mechanisms and current status
Rep. Prog. Phys. 75 076502
[2] Ielmini D 2016 Resistive switching memories based on
metal oxides: mechanisms, reliability and scaling
Semicond. Sci. Technol. 31 063002
[3] Linn E, Rosezin R, Kügeler C and Waser R 2010
Complementary resistive switches for passive nanocrossbar
memories Nat. Mater. 9 403–6
[4] Wu S and Li S 2015 Compliance current dependence of
conversion between bipolar, unipolar, and threshold
resistance switching in Mn3O4 films AIP Adv. 5 087154
[5] Peng H Y, Li Y F, Lin W N, Wang Y Z, Gao X Y and Wu T
2012 Deterministic conversion between memory and
threshold resistive switching via tuning the strong electron
correlation Sci. Rep. 2 442
[6] Huang Y J, Chao S C, Lien D H, Wen C Y, He J H and
Lee S C 2016 Dual-functional memory and threshold
resistive switching based on the push–pull mechanism of
oxygen ions Sci. Rep. 6 23945
[7] Lee J Y, Baek Y J, Hu Q, Choi Y J, Kang C J, Lee H H,
Kim H M, Kim K B and Yoon T S 2013 Multimode
threshold and bipolar resistive switching in bi-layered
Pt Fe2O3 core-shell and Fe2O3 nanoparticle assembly
Appl. Phys. Lett. 102 122111
[8] Sun H, Liu Q, Li C, Long S, Lv H, Bi C, Huo Z, Ling L and
Liu M 2014 Direct observation of conversion between threshold
switching and memory switching induced by conductive
filament morphology Adv. Funct. Mater. 24 5679–86
[9] Jo S H, Kumar T, Narayanan S and Nazarian H 2015 Cross-
point resistive RAM based on field-assisted superlinear
threshold selector IEEE Trans. Electron Devices 62 3477–81
[10] Song J, Woo J, Prakash A, Lee D and Hwang H 2015
Threshold selector with high selectivity and steep slope
for cross-point memory array IEEE Electron Device Lett.
36 681–3
[11] Lee M J et al 2007 Two series oxide resistors applicable
to high speed and high density nonvolatile memory
Adv. Mater. 19 3919–23
[12] Song J, Woo J, Lee S, Prakash A, Yoo J, Moon K and
Hwang H 2016 Steep slope field-effect transistors with
Ag/TiO2-based threshold switching device IEEE Electron
Device Lett. 7 932–4
[13] Shukla N, Thathachary A V, Agrawal A, Paik H, Aziz A H,
Schlom D G, Gupta S K, Engel-Herbert R and Datta S 2015
A steep-slope transistor based on abrupt electronic phase
transition Nat. Commun. 6 7812
[14] Ramadoss A, Krishnamoorthy K and Kim S J 2012 Facile
synthesis of hafnium oxide nanoparticles via precipitation
method Mater. Lett. 75 215–7
[15] Jayaraman V, Bhavesh G, Chinnathambi S, Ganesan S and
Aruna P 2014 Synthesis and characterization of hafnium
oxide nanoparticles for bio-safety Mater. Express 4 375–83
[16] Xiong S, Qi W, Huang B, Wang M and Wei L 2011 Gibbs
free energy and size temperature phase diagram of hafnium
nanoparticles J. Phys. Chem. C 115 10365–9
[17] Sawa A 2008 Resistive switching in transition oxides
Mater. Today 11 28–36
J. Phys. D: Appl. Phys. 50 (2017) 045103
[18] Quesnel E, Pauliac-Vaujour E and Muffato V 2010 Modeling
metallic nanoparticle synthesis in a magnetron-based
nanocluster source by gas condensation of a sputtered vapor
J. Appl. Phys. 107 054309
[19] Valov I, Linn E, Tappertzhofen S, Schmelzer S, Van Den Hurk J,
Lentz F and Waser R 2013 Nanobatteries in redox-based
resistive switches require extension of memristor theory
Nat. Commun. 4 1771
[20] Bousoulas P, Michelakaki I and Tsoukalas D 2014 Influence
of Ti top electrode thickness on the resistive switching
properties of forming free and self-rectified TiO2−x thin
films Thin Solid Films 571 23–31
[21] Bousoulas P, Stathopoulos S, Tsialoukis D and Tsoukalas D
2016 Low-power and highly uniform 3b multilevel switching
in forming free TiO2−x based RRAM with embedded Pt
nanocrystals IEEE Electron Device Lett. 37 874–7
[22] Kofstad P 1972 Nonstoichiometry, Diffusion and Electrical
Conductivity in Binary Metal Oxides (New York: Wiley)
(doi: 10.1002/maco.19740251027)
[23] Yang J J, Strachan J P, Miao F, Zhang M X, Pickett M D,
Yi W, Ohlberg D A A, Medeiros-Ribeiro G and
Williams R S 2011 Metal/TiO2 interfaces for memristive
switches Appl. Phys. A 102 785–9
[24] Yang J J, Pickett M D, Li X, Ohlberg D A A, Stewart D R
and Williams R S 2008 Memristive switching mechanism
for metal/oxide/metal nanodevices Nat. Nanotechnol.
3 429–33
[25] Huang J J, Kuo C W, Chang W C and Hou T H 2010
Transition of stable rectification to resistive-switching in Ti/
TiO2/Pt oxide diode Appl. Phys. Lett. 96 262901
[26] Lim E W and Ismail R 2015 Conduction mechanism of
valence change resistive switching memory: a survey
Electronics 4 586–613
[27] Park S G, Köpe B M and Nishi Y 2010 Electronic correlation
effects in reduced rutile TiO2 within the LDA  +  U method
Phys. Rev. B 82 115109
[28] Valov I, Waser R, Jameson J R and Kozicki M N 2011
Electrochemical metallization memories: fundamentals,
applications, prospects Nanotechnology 22 289502
[29] Pan F, Chen C, Wang Z S, Yang Y C, Yang J and Zeng F 2010
Nonvolatile resistive switching memories-characteristics,
mechanisms and challenges Prog. Nat. Sci. 20 1–15
[30] Lübben M, Karakolis P, Ioannou-Sougleridis V, Normand P,
Dimitrakis P and Valov I 2015 Graphene-modified interface
10
I Michelakaki et al
controls transition from VCM to ECM switching modes in
Ta/TaOx based memristive devices Adv. Mater. 27 6202–7
[31] Wedig A et al 2016 Nanoscale cation motion in TaOx, HfOx
and TiOx memristive systems Nat. Nanotechnol. 11 67–74
[32] Privitera S, Bersuker G, Butcher B, Kalantarian A,
Lombardo S, Bongiorno C, Geer R, Gilmer D C and
Kirsch P D 2013 Microscopy study of the conductive
filament in HfO2 resistive switching memory devices
Microelectron. Eng. 109 75–8
[33] Hsiung C P, Liao H W, Gan J W, Wu T B, Hwang J C, Chen F
and Tsai M J 2010 Formation and instability of silver
nanofilament in Ag-based programmable metallization cells
ACS Nano 4 5414–20
[34] Tsunoda K, Fukuzumi Y, Jameson J R, Wang Z, Griffin P B
and Nishi Y 2007 Bipolar resistive switching in
polycrystalline TiO2 films Appl. Phys. Lett. 90 113501
[35] Liu Q, Long S, Lv H, Wang W, Niu J, Huo Z, Chen J and
Liu M 2010 Controllable growth of nanoscale conductive
filaments in solid-electrolyte-based ReRAM by using a
metal nanocrystal covered bottom electrode ACS Nano
4 6162–8
[36] Hu C, McDaniel M D, Posadas A, Demkov A A, Ekerdt G
and Yu E T 2014 Highly controllable and stable quantized
conductance and resistive switching mechanism in
single-crystal TiO2 resistive memory on silicon Nano Lett.
14 4360–7
[37] Goux L and Valov I 2016 Electrochemical processes and
device improvement in conductive bridge RAM cells Phys.
Status Solidi a 213 225–482
[38] Acha C, Monteverde M, Nunez-Regueiro M, Kuhn A and
Franco M A A 2003 Electrical resistivity of the Ti4O7
magneli phase under high pressure Eur. Phys. J. B 34 421–8
[39] Rahaman S Z, Maikap S, Tien T C, Lee H Y, Chen W S,
Chen F T, Kao M J and Tsai M J 2012 Excellent resistive
memory characteristics and switching mechanism using a
Ti nanolayer at the Cu/TaOx interface Nanoscale Res. Lett.
7 345
[40] Yang Y C, Pan F and Zeng F 2010 Bipolar resistance
switching in high-performance Cu/ZnO: Mn/Pt nonvolatile
memories: active region and influence of Joule heating
New J. Phys. 12 023008
[41] Yu S, Guan X and Philip Wong H S 2011 Conduction
mechanism of TiN/HfOx/Pt resistive switching memory: a
trap-assisted-tunneling model Appl. Phys. Lett. 99 063507