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IEEE TRANSACTIONS ON ELECTRON DEVICES
Low-Power Forming Free
TiO2–x /HfO2–y /TiO2–x -Trilayer RRAM Devices
Exhibiting Synaptic Property Characteristics
Panagiotis Bousoulas, Irini Michelakaki, Evangelos Skotadis,
Menelaos Tsigkourakos, and Dimitris Tsoukalas
Abstract — The insertion of an HfO2−y layer within
TiO2−x /HfO2−y /TiO2−x resistive random access mem-
ory (RRAM) yields in low set power of 50 nW (10 nA at 5 V),
low reset power of 3 nW (1 nA at −3 V), and good cycling
variability (σ /μ < 0.5). In addition, under pulse experiments,
fast switching time of 1 μs, good 107 cycling endurance and
retention performance at 150 °C, was demonstrated. The
confinement of the switching effect into the HfO2−y film,
which has the highest oxygen content and deeper oxygen
vacancy energy levels compared with the adjusting two
layers of TiO2−x which act as two series resistances, can
explain the low switching energy. The gradual modulation
of the resistance permits also the manifestation of long-
term potentiation synaptic plasticity, induced by the appli-
cation of a train of pulses with different repetition intervals.
A quantitative model was applied in order to reproduce the
analog SET/RESET responses of the trilayer configuration
and highlight the role of the local distribution of oxygen
vacancies. These effects in conjunction with the room
temperature fabrication process used and the forming-free
nature of the thin films are considered as an optimization
route toward high-density RRAM design.
Index Terms — Conducting filaments (CFs), diffusion
barrier, oxygen content, oxygen ion reservoir, sputtering,
thin films, trilayer.
I. I NTRODUCTION
T HE continuous scaling of the semiconductor devices
will ultimately push the conventional FLASH memories
into their physical limits. So, it is urgent to come up with
new memory concepts which will deal with the demanding
list of prerequisites that nonvolatile memories should satisfy.
Resistance switching effect is arising as one of the most
suitable candidates for the post FLASH era, mainly due to
its simple structure [1]. Although several questions remain
Manuscript received April 11, 2017; accepted May 23, 2017. The
work of P. Bousoulas and D. Tsoukalas was supported by Research
Projects for Excellence IKY (State Scholarship Foundation)/SIEMENS.
The review of this paper was arranged by Editor U. E. Avci.
(Corresponding author: Panagiotis Bousoulas.)
The authors are with the Department of Physics, School of Applied
Sciences, National Technical University of Athens, 15773 Athens,
Greece (e-mail: panbous@mail.ntua.gr; michelakaki.irini@gmail.com;
evskotad@mail.ntua.gr; mxtsig@gmail.com; dtsouk@central.ntua.gr).
Color versions of one or more of the figures in this paper are available
online at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TED.2017.2709338
0018-9383 © 2017 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
1
to be answered about the physical mechanisms underlying
device operation, for the realization of crossbar arrays the most
impeding tasks are the low operating currents and selector
device issues. The latter seems to be successfully dealt with the
one transistor-one resistor architecture [2], while low-current
operation (in the nanoampere range) remains challenging,
mainly due to reliability concerns [3]. One possible way to
improve the switching performance is to use different layers
of metal oxides, each of them being assigned to satisfy
a specific goal. Thus, we have the opportunity to confine
the switching effect into one layer, reducing the degree of
inherent variability, and at the same time creating another
layer with high concentration of oxygen vacancies, which
will serve the role of a series resistance, eliminating there-
fore the need for external compliance control. In addition,
these layers can act as oxygen vacancy reservoirs, success-
fully sustaining the memory effect under consecutive device
operation and reducing the switching currents. These con-
cepts have been effectively implemented in bilayer structures,
resulting in low-power switching performance with promising
uniformity [4]–[6].
In this paper, we report the fabrication of a trilayer structure
with the following configuration: TiO2−x /HfO2−y /TiO2−x , not
studied before. Comparing with devices with three layers
of switching materials that have been reported in [7]–[9]
here we show that it is possible by a proper control of the
degree of stoichiometry of the component materials to achieve
low-power random access memory (RRAM) performance
with self-compliance and enhanced uniformity characteristics,
applying the same concept which we have recently explored
in bilayer configurations [10]. For comparison, standalone
TiO2−x , HfO2−y and bilayer TiO2−x /HfO2−y devices were
fabricated in order to investigate the influence of each layer
on the switching effect. Our results show that the SET/RESET
current values are remarkably reduced in the trilayer structure,
and the cycling uniformity has been improved. The low oxygen
content of the TiO2−x films creates a set of two series resis-
tances which together with the deeper energy levels of oxygen
vacancies reported in the HfO2−y film, are the key issues for
the low switching energy operation. In addition, by taking
advantage of the gradual switching pattern, we demonstrate
that these devices can emulate neuromorphic properties which
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2 IEEE TRANSACTIONS ON ELECTRON DEVICES
are considered the basic mechanism for memory and self-
learning. A physical model was also implemented in order to
understand the gradual switching pattern at low operating cur-
rent (∼nanoampere). Based on the conducting filament (CF)
conjecture, regions with high density of oxygen vacancy
density (TiO2−x ) can switch the device from a high-resistance
state (HRS) to a low-resistance state (LRS), while the presence
of the HfO2−y layer can affect the energy diffusion barrier
for oxygen vacancy migration, therefore directly influencing
the drift and diffusion fluxes. The enhanced diffusivity of the
HfO2−y layer could be attributed to its crystalline nature as it
has been confirmed by X-ray diffraction (XRD) measurements,
in contrast with TiO2−x layer that was found in amorphous
configuration. The decisive role of the energy diffusion barrier
value was also investigated by the simulation methodology,
revealing good agreement with the experimental data.
II. D EVICE FABRICATION AND E LECTRICAL
C HARACTERIZATION
A. Experiment
The thin film deposition technique is based on a
physical vapor deposition process integrated in a high-
vacuum system. All the following processes were carried
out at room temperature. Four set of devices were fab-
ricated: the first one was TiN/Ti/TiO2−x /Au with 45-nm
thickness of the TiO2−x film, the second one was the
TiN/Ti/HfO2−y /Au with 45-nm thickness of the HfO2−y
layer, the third was TiN/Ti/HfO2−y /TiO2−x /Au with each
layer to have 22.5-nm thickness, and the fourth was
TiN/Ti/TiO2−x /HfO2−y /TiO2−x /Au with again each layer to
have 22.5-nm thickness. All devices were integrated on
SiO2 /Si substrates. The 40-nm Au bottom electrode (BE),
which was deposited by e-gun evaporation, as well as the 4-nm
Ti and 40-nm TiN top electrodes (TEs), which were deposited
with RF sputtering (using Ti and TiN targets, respectively),
was the same for all devices. The titanium oxide layer was
deposited by reactive RF magnetron sputtering using a high-
purity Ti target (99.9% purity) at room temperature under
low oxygen content (1.5 sccm-13%), while for the hafnium
oxide we have used ceramic HfO2 target in combination
with high oxygen content (5 sccm-33.3%) during sputtering.
The argon flow was maintained constant at 10 sccm in all
cases. The devices were patterned to form metal–insulator–
metal capacitors, using lift-off lithography. The size of each
square TE was 100 ×100 μm2 . Electrical characterization was
performed with Keithley 4200 SCS, by applying all signals
to the TE and keeping the BE grounded. XRD measurements
were also carried out in order to assess the structural properties
of the deposited films.
B. XRD Measurements
Fig. 1(a) depicts the results of the XRD measurements,
employed on the single layers of TiO2−x and HfO2−y , by using
the standard θ –2θ method. The TiO2−x film was found in
the amorphous state, which is expected due to the very low
oxygen content, in accordance with our previous work [11].
On the other hand, several peaks related to monoclinic phase
Fig. 1. XRD patterns of the (a) as-grown TiO2−x and HfO2−y single
layers and (b) TiO2−x /HfO2−y bilayers, at room temperature.
Fig. 2. (a) I–V characteristics for the single-layer samples, revealing the
transition between the HRS (forward sweep) and LRS (backward sweep).
The arrows and the numbers in the graph indicate the voltage sweep
direction. Similar responses were recorded by starting the sweeps from
0 V to |Vmax | (not shown here), corroborating the completely forming-free
nature of our devices. (b) Hysteresis curves under consecutive cycling
operation for the HfO2−y RRAM device.
were detected, which is anticipated due to the high oxygen
content despite the room temperature deposition process [12].
These peaks indicate the creation of small crystallites, which
facilitate the migration of ionic species, mainly through grain
boundaries. The films present columnar structure with high
aspect ratio, similar with those reported elsewhere [11].
These peaks are also present in the bilayer configuration [13]
[Fig. 1(b)], suggesting that their presence would still influence
the transport properties of oxygen vacancies. In addition,
the existence of regions within the device active core with
high degree of crystallinity suggests the possibility to confine
the switching effect into specific locations and thus narrow
down the well-known nonuniformity issue. This effect is
even more obvious in the trilayer arrangement, since we can
obtain reliable switching performance with low variation of
the electrical outputs (Section III-C). The XRD spectra of the
trilayer structure is similar to that of the bilayer one (not shown
here), while the impact of the crystallinity of the HfO2−y layer
will be discussed in more detail within the simulation results
(Section III).
C. Electrical Characterization Evaluations
In order to examine the electrical performance of the
devices, direct current (dc) measurements under voltage sweep
loops were carried out, at single layers of TiO2−x and HfO2−y
with same thickness and different oxygen content. The results
are depicted at Fig. 2, where we can observe the different
response of the two materials, which is mainly attributed to the
existence of fewer number of oxygen vacancies within HfO2−y
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BOUSOULAS et al.: LOW-POWER FORMING FREE TiO2-X /HfO2−Y /TiO2−X -TRILAYER RRAM DEVICES
Fig. 3. I–V hysteresis curves of the (a) Ti/TiO2−x /Au,
(b) Ti/HfO2−y /TiO2−x /Au, and (c) Ti/TiO2−x /HfO2−y /TiO2−x /Au
devices. The arrows in the graphs indicate the switching direction.
Similar responses were recorded by starting the sweeps from 0 V to
|Vmax | (not shown here).
as has been ascertained by chemical analysis results [14], [15],
resulting in low operating current values. We have to underline
the forming-free operation of both devices as well as the
self-compliance behavior which was captured for the case of
HfO2−y , in contrast with the TiO2−x layer where a compliance
current (Icc ) of 10 mA was constantly enforced.
The transitions from the HRS to the LRS (SET process)
and vice versa (RESET process) are gradual for both cases,
denoting the great advantages that our devices offer toward
neuromorphic applications, as we will demonstrate later. Also,
the Ti-top capping layer is considered to greatly assist the
resistive switching effect, facilitating the redox reactions at
the interface between the TE/dielectric through the formation
of an ionic reservoir [16]. It is also interesting to notice that
in the hysteresis spectra of HfO2−y at about ±1 V appear two
peaks, which are ascribed to the intermediate concentration
of oxygen vacancies [17] and the potential existence of weak
ferroelectricity effect [18].
In Fig. 3(a)–(c), we present the dc current–voltage (I –V )
hysteresis loops of the single-layer, bilayer, and trilayer struc-
tures, respectively, whereas again all devices operate without
applying any electro-forming process. Three clear distinct
patterns are observed for each device configuration. For the
single-layer memory cells, although switching effect takes
place at 4-V bias, the operating currents are high for both
SET/RESET transitions (10 and 1 mA, respectively). In addi-
tion, the consecutive cycling operation degrades the memory
performance, retaining, however, an ON/ OFF ratio of one order
of magnitude. This behavior could be attributed to the presence
of high number of oxygen vacancies within the device active
core, due to the low oxygen content during the fabrication
process, which lead to the formation of extended defect regions
3
Fig. 4. Schematic representation of the proposed switching mechanism
for (a) single-layer, (b) bilayer, and (c) trilayer memristors.
that cause impartial rupture of the CFs and progressive shift of
the HRS to LRS. So, we can argue that these devices operate
like a resistor, while the pure memristive behavior originates
from the migration of a small amount of oxygen vacancies,
as it is depicted in Fig. 4(a). The smooth and not abrupt
transitions that are recorded for both SET/RESET processes
could also support our argument, since the high availability
of the potential percolating CF paths imposes this gradual
character.
On the contrary, a different switching picture is captured
when the thin layer of HfO2−y is present. Although the
dc bias has been slightly increased to 5 V, in order to
achieve stable memory performance, the operating currents
have been reduced about four orders of magnitude. Besides,
an improvement for both HRS and LRS distributions, in terms
of cycling stressing, has been recorded, sustaining a memory
ratio of 102 . We have also to underline the self-compliance
behavior, in contrast with the single-layer device where an
Icc of 10 mA was constantly applied. Also, comparing with
the single layer of HfO2−y RRAM devices, the bilayer ones
present even low operating current values, at about one order
of magnitude, bigger memory window and no parasitic peaks
appear at ±1 V.
The combination of the following two effects could interpret
the above results. The first one is the confinement of the
switching effect within the HfO2−y , which has the high oxygen
content, while the rest of the film—TiO2−x —behaves like a
pure resistor [Fig. 4(b)]. Thus, the main voltage drop takes
place at the top layer, justifying the lower switching cur-
rents [19]. Furthermore, the mismatch of the oxygen vacancy
energy levels could explain the low current values, since in
TiO2−x oxygen vacancies create very shallow levels (∼0.3 eV
below the conduction band) [20] in contrast with HfO2−y
where deeper energy levels are induced by the presence of the
oxygen vacancies (∼0.9 eV) [21]. Thus, electron movement
between HfO2−y and the electrode, performed via a trap/detrap
processes [22], requires a larger activation energy, since the
transmission probability of the trap-assisted-tunneling mecha-
nism (which is implied by the gradual switching process) has
a strong dependence from the energy trap levels [23]. The
use of a second layer of TiO2−x above the HfO2−y film,
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4 IEEE TRANSACTIONS ON ELECTRON DEVICES
Fig. 5. (a) Cumulative distribution functions of the LRS and HRS
responses. (b) Pulse endurance measurements under the application of
±5 V/1 μs square voltage pulses. (c) Retention measurements at room
and elevated temperatures. The filled symbols correspond to the LRS
and the open to the HRS (read voltage 1 V).
in a trilayer configuration, results in even lower operating
currents (∼10 nA) and higher switching ratio (∼103), since
larger amount of voltage drop takes place on the HfO2−y layer
[Fig. 4(c)], due to the presence of two series resistances. The
slightly bigger variations in trilayer structures with respect to
bilayer are due to the fluctuations related with the very low
operating current operation. We have to remark that in reality
the situation could be more complex, since the relative energy
trap level depth depends on the interfacial band offsets and
therefore the effects on the hysteresis responses could be more
subtle.
The cumulative probability graph in Fig. 5(a) reveals the
distribution of the both HRS and LRS, for the three device
architectures. A significant improvement of temporal unifor-
mity is recorded for the bilayer and trilayer memory cells.
(50 different devices per sample were tested.) As it con-
cerns LRS, a clear drop of resistance values variations is
recorded (coefficient of variance ∼0.4), while a similar pattern
is recorded for the HRS (coefficient of variance ∼0.6–0.7).
The restriction of the possible regions for CF formation within
the HfO2−x is the major reason for this improvement. The
values of resistances of both LRS/HRS distributions in the tri-
layer configuration have been reduced at about 107 /108 orders
of magnitude, with respect to the single TiO2−x layer device,
respectively, revealing a simple way to tune the device resis-
tance over several orders of magnitude. The switching speed
was also examined by applying pulses with 1 μs width and
amplitude of ±5 V, in order to impose the SET/RESET
transitions, as it is depicted at Fig. 5(b). Also, 107 SET/RESET
cycles were enforced on fresh memory cell, as it can be seen
at Fig. 5(b), resulting in a switching ratio of 10 in any case.
Charge retention measurements were also performed at room
and elevated temperatures [Fig. 5(c)]. While at room temper-
ature there is no severe degradation for each memory state
Fig. 6. Measured transient current responses (blue line) as a function
of time during SET process in the trilayer RRAM, under the applica-
tion of various SET pulses (VSET -black line) with amplitude ranging
from (a) 5 to (d) 8 V and fixed width 1 μs. (e) Calculated transient current
response for the case of 8-V pulse amplitude.
during time over 105 s, at 150 °C there are slight perturbations
for both HRS/LRS due to enhanced migration rates of oxygen
ions and oxygen vacancies and the concomitant variations they
impose into the CF continuity, on the SET process, and broken
region, on the RESET process. Nevertheless, a switching ratio
of ∼50 is maintained, preserving the distinguished nature of
the two resistance states.
The switching kinetics were also examined for the tri-
layer configuration by varying the amplitude of vSET-Pulse ,
as can be discerned from Fig. 6(a)–(d), while the calculated
transient profile [Fig. 6(e)] was estimated by the simulation
methodology, which will be presented at the following section.
At the beginning of the pulse the current response is low,
but after a period of time it gradual increase, while the
corresponding time is defined as tSET switching time. For the
smaller vSET−Pulse(4.5 V) a higher tSET (∼10 μs) is required
to switch the memory cell into the LRS whereas a shorter tSET
(∼40 ns) has been captured for higher vSET−Pulse (8 V). Sev-
eral measurements have been conducted in a wide range of
vSET-Pulse , ranging from 4.5 to 8 V with 100-mV step. The
outcome is presented at Fig. 7, divulging a direct connection
between the vSET-Pulse and the tSET and a relatively steep slope
of about 0.61 V/dec(s), while similar values have been reported
for other systems [24]–[26]. This high nonlinearity on the
SET switching kinetics could be attributed to field and local
temperature accelerated migration of oxygen vacancies, since
the ion hopping presents a strong nonlinear relation from these
two driving forces [27]. In addition, at Fig. 8, we present the
measured and calculated current profiles for vRESET−Pulse of
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BOUSOULAS et al.: LOW-POWER FORMING FREE TiO2-X /HfO2−Y /TiO2−X -TRILAYER RRAM DEVICES
Fig. 7. Dependence of the SET time (tSET ) as a function of the pulse
amplitude, denoting the high nonlinearity of the SET kinetics.
Fig. 8. (a) Measured and (b) calculated transient current responses
(blue line) as a function of time during RESET process in the trilayer
RRAM, under the application of −8 V RESET pulse (VRESET -black line)
and fixed width 1 μs.
−8 V and width 1 μs, while now the tRESET is defined as
the time required in order to observe a clear reduction on the
measured current.
III. M ODELING
From the above analysis, it is clear that the underlying
switching mechanism has a strong influence from the local
concentration of oxygen vacancies, since they act as mobile
donors [28] and significantly alter the electrical and thermal
conductivity values. Regions with elevated levels of cluster-
ing oxygen vacancies form CFs, which are responsible for
the alteration of the resistance. The filamentary conjecture
is mainly relied on the insensitivity of the LRS from the
device area, obtaining similar results for the trilayer config-
uration with those reported in our previous works (not shown
here) [10], [16]. Thus, a physical model was employed in order
to shed light in the memory performance of the trilayer device.
The simulation begins after the CF has already been formed,
whereas the simulated geometry is presented at Fig. 9(a).
The CF has 4-nm diameter and 45-nm length. A smaller
CF was introduced within HfO2−y layer, since it contains a
lower density of oxygen vacancies with respect to the other
two layers of TiO2−x , and therefore is anticipated the main
voltage drop and temperature increase to take place there,
given that the driving forces for the resistance switching is the
field and temperature induced migration of oxygen vacancies.
Therefore, the total memristive behavior can be predicted by
5
Fig. 9. (a) Cross section of the simulated cell during SET/REST
processes. A uniform defect density nD = 1 × 1022 cm−3 was defined
within the reservoir layer (TiO2−x ) as well as the CF region. (b) Measured
and calculated I–V characteristics.
the drift-diffusion, carrier continuity, and Joule heating partial
differential equations, which were solved self-consistently with
a numerical solver (COMSOL) [29]–[31]
∂n D
= ∇ · (D∇n D − v · n D ) + G (1)
∂t
∇ · σ ∇ψ = 0 (2)
−∇ · kt h ∇T = J · E (3)
where n D is the concentration of oxygen vacancies, D =
(1/2) · a 2 · v0 · exp(−(E a /k B T )) is the diffusivity, a is the
effective hopping distance (0.1 nm), v0 is the attempt-to-escape
frequency (1013 Hz), k B is Boltzmann’s constant, T is the tem-
perature, ψ is the electric potential, E a is the diffusion barrier
migration
for ion migration E a = E a , v = a·v0 ·exp(−(E a /k B T ))·
sinh((Q Ea/2k B T )) is the drift velocity of oxygen vacancies,
E is the electric field, and Q is the ionic charge (2q) and
G = n G exp(−(E b − qa E)/k B T ) is the generation rate of
oxygen vacancies (used only at SET process −E B = 1 eV).
In order to solve the set of equations self-consistently, inputs
for electrical conductivity (σ ) and thermal conductivity (kth )
are required. A detailed analysis of the simulation procedure
can be found in our previous work [32]. As regards the diffu-
sivity activation energy values, we have used 1 eV for HfO2−y
and 1.5 eV for TiO2−x , in order to attain good agreement with
the experimental data. However, our assumption is compatible
with the XRD spectra of the different materials, since the
existence of grain boundaries within HfO2−y layer should
decisively affect the ionic diffusivity, as has been pointed out in
both theoretical [33], [34] and experimental studies [35], [36].
Even though, we cannot exclude the possibility of segregation
of point defects at grain boundaries, the application of an elec-
tric field facilitates the migration of positively charged oxy-
gen vacancies though grain boundaries [37], impacting thus
directly the electronic properties of the trilayer configuration,
in terms of enhanced uniformity. The used values of diffusion
energy barrier are also comparable with those reported in
similar approaches [29]–[31], as well as with those obtained
through theoretical studies [38]–[40]. Fig. 9(a) displays the
simulated geometry whereas Fig. 9(b) shows the measured and
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6 IEEE TRANSACTIONS ON ELECTRON DEVICES
Fig. 10. Measured conductance changes at (a) single-layer,
(b) bilayer, and (c) trilayer samples under the application of ±5, ±8, and
±10 V pulses, respectively, with 10-ms width and repetition intervals.
calculated I –V characteristics during SET/RESET transitions,
respectively. The simulation profiles can capture the gradual
character of the switching effect, while the physical picture
can be viewed as the filling/depleting of a broken region
within the CF and near the TE, with oxygen vacancies. The
origins of the gradual responses can be found to the different
dependence of the drift velocity and diffusivity from the
local electric field and temperature. The RESET transition
begins at about −2 V and the current gradually decreases,
achieving a difference of about one order of magnitude after
vRESET = −5 V. The physical origin for this effect is the
creation of a small tunneling gap (∼1–2 nm) near the TE,
which causes the decrease in the current values and enhanced
locally the temperature and electric potential. In contrast,
during SET transition, the continuum of the CF is restored due
to the redistribution of oxygen vacancies, causing the decrease
of the local temperature.
The gradual switching behavior, which is recorded for both
SET and RESET transitions, offers also great advantages
for synaptic learning rules such as spike-timing dependent
plasticity (STDP). In order to investigate whether all the pro-
posed configurations can be used as synaptic devices, we have
measured the conductance change after the application of a
consecutive train of 15 SET/RESET pulses, with constant
width and repetition interval of 10 ms. The amplitude of the
prespike pulses was +5, +8, and +10 V, for the single-layer,
bilayer, and trilayer memristor devices, respectively, whereas
−5, −8, and −10 V were selected for the postspike pulses.
As it can be seen form Fig. 10(a)–(c), all devices potenti-
ate (increase in conductance) after each pulse is applied, while
depress (decrease in conductance) when a train of 15 RESET
Fig. 11. Relative change of conductance ΔG/G as a function of pulse
delay Δt.
Fig. 12. Conductance changes in the trilayer structure after the appli-
cation of 10 V/10 ms voltage pulses, with different repetition intervals.
pulses is applied on the same memory cell, with the same
characteristics and negative amplitude. Also, it is interesting
to notice that we have demonstrated synaptic behavior over
six orders of magnitude conductance value, indicating the
possibility to tune by our approach the levels of synaptic
learning. Similar results were obtained by measuring different
cells on the same samples, denoting the improvement of the
spatial uniformity of the bilayer and trilayer structures, with
respect to single layer, which exhibits big fluctuations. These
results are similar to the long-term potentiation (LTP) effect
which has been observed in biological synapses.
Fig. 11 depicts the normalized conductance change G/G
as a function of pulse timing t for all samples, during
the first train of ±15 V SET/RESET pulses, demonstrating
STDP performance. Nevertheless, when the repetition interval
is being reduced to 1 ms, a sudden increase of the conductance
takes place after six consecutive pulses, while when the time
interval is reduced to 0.1 ms, the same abrupt transition
appears after four pulses, as it is depicted in Fig. 12. (The data
are related with the trilayer devices.) These sudden transitions
resemble the LTP mechanism, which has been reported in
biological synapses [41]. The origins for these analog effects
seem to be closely related with the processes of CF forma-
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BOUSOULAS et al.: LOW-POWER FORMING FREE TiO2-X /HfO2−Y /TiO2−X -TRILAYER RRAM DEVICES
tion/annihilation [10]. If we consider that oxygen vacancies act
as mediators for the electronic conduction, through trap/detrap
processes of electrons, the interplay between the two driving
fluxes (drift and diffusion) dictates the switching pattern [42].
During SET transition, both fluxes have the same direction,
with drift to outweigh diffusion, due to the strong dependence
from the electric field and local temperature. The relatively
high diffusion energy barriers in both TiO2−x and HfO2−y
layers result in low diffusivity, which also strongly depends
from the temperature, and therefore a smooth transition is
recorded for both ac and dc signals. However, when the
interval time is reduced, heat cannot be quickly removed, and
a more abrupt transition takes place. On the other hand, during
RESET process always a gradual transition is observed, since
now the two fluxes have opposite directions and to some extent
they cancel each other. So, tuning the balance between drift
and diffusion fluxes is a key factor toward analog memristive
behavior.
IV. C ONCLUSION
In summary, low-power resistive switching behavior was
demonstrated in trilayer structures, with good endurance prop-
erties and retention performance. The use of a stack of metal
oxide layers with different oxygen contents as well as the
discrepancy between oxygen vacancy energy levels is regarded
as the two key factors for this performance. The existence of
crystalline peaks in the XRD spectra in the bilayer and tri-
layer configurations indicate the existence of grain boundaries
within HfO2−y layer, which can affect the transport properties
of oxygen vacancies by tuning the diffusion barrier values.
The latter was nicely captured by a quantitatively approach
which was deployed in order to interpret the switching effect
in trilayer RRAM, by calculating self-consistently the distrib-
utions of local electric field, temperature, and oxygen vacancy
concentration. The strong competition between drift velocity
and diffusivity dictates the analog switching pattern, which
was recorded in our devices and can be effectively tuned
by choosing materials with differences in physical properties
(i.e., diffusion barrier and hopping distance). The gradual
transitions are also high attractive for multilevel switching
and neuromorphic applications. Concerning the latter issue,
synaptic plasticity functions were also implemented by varying
the voltage pulse amplitudes and intervals, divulging that these
devices can emulate several features of biological synapses.
ACKNOWLEDGMENT
The authors would like to thank Dr. G. Kokkoris
from the Institute of Nanoscience and Nanotechnology of
NCSR Demokritos for his help regarding simulations.
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8 IEEE TRANSACTIONS ON ELECTRON DEVICES

[25] F. Alibart, L. Gao, B. D. Hoskins, and D. B. Strukov, “High precision Panagiotis Bousoulas received the B.Sc. and
tuning of state for memristive devices by adaptable variation-tolerant M.Sc. degrees in applied physics and microsys-
algorithm,” Nanotechnology, vol. 23, no. 7, pp. 075201-1–075201-20, tems and nanotechnology from the National
2012. Technical University of Athens, Athens, Greece,
[26] M. G. Cao et al., “Nonlinear dependence of set time on pulse voltage in 2010 and 2012, respectively, where he is
caused by thermal accelerated breakdown in the Ti/HfO2 /pt resistive currently pursuing the Ph.D. degree in nanotech-
switching devices,” Appl. Phys. Lett., vol. 101, pp. 203502-1–203502-5, nology and emerging memories.
Nov. 2012.
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K. Shiraishi, “Vacancy cohesion-isolation phase transition upon charge
injection and removal in binary oxide-based RRAM filamentary- Irini Michelakaki received the Diploma degree
type switching,” IEEE Trans. Electron Devices, vol. 60, no. 10, in applied physics from the School of Applied
pp. 3400–3406, Oct. 2013. Mathematics and Physics, National Technical
[29] S. Larentis, F. Nardi, S. Balatti, D. C. Gilmer, and D. Ielmini, “Resis- University of Athens (NTUA), Athens, Greece,
tive switching by voltage-driven ion migration in bipolar RRAM— in 2005, and the M.Sc. degree in microelectronics
Part II: Modeling,” IEEE Trans. Electron Devices, vol. 59, no. 9, and optoelectronics from the University of Crete,
pp. 2468–2475, Sep. 2012. Heraklion, Greece, in 2009. She has been pur-
[30] S. Kim et al., “Physical electro-thermal model of resistive switching suing the Ph.D. degree with the Department of
in bi-layered resistance-change memory,” Nature Sci. Rep., vol. 3, Physics, NTUA, since 2011.
pp. 1680-1–1680-6, Apr. 2013. From 2006 to 2011, she was involved in various
[31] S. Kim, S.-H. Choi, and W. Lu, “Comprehensive physical model of research projects.
dynamic resistive switching in an oxide memristor,” ACS Nano, vol. 8,
no. 3, pp. 2369–2376, Feb. 2014.
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ing of the SET/RESET characteristics and analog properties of Evangelos Skotadis received the bachelor’s
TiO x /HfO2−x /TiO x -based RRAM devices,” in Proc. Int. Conf. degree from the School of Applied Mathematics
Simulation Semiconductor Process. Devices (SISPAD), Sep. 2016, and Physics, National Technical University of
pp. 249–252. Athens (NTUA), Athens, Greece, in 2007, the
[33] K. McKenna and A. Shluger, “The interaction of oxygen vacancies with master’s degree under the Microsystems and
grain boundaries in monoclinic HfO2 ,” Appl. Phys. Lett., vol. 95, no. 22, Nanodevices M.Sc. program of NTUA, in 2009,
pp. 222111-1–222111-3, Dec. 2009. and the Ph.D. degree from the School of Applied
[34] K.-H. Xue et al., “Grain boundary composition and conduction in Mathematics and Physics, NTUA, in 2014.
HfO2 : An ab initio study,” Appl. Phys. Lett., vol. 102, no. 20, He is currently a Post-Doctoral Researcher
pp. 201908-1–201908-4, May 2013. with NTUA.
[35] G. Knoner, K. Reimann, R. Rower, U. Sodervall, and
H.-E. Schaefer, “Enhanced oxygen diffusivity in interfaces of
nanocrystalline ZrO2 ·Y2 O3 ,” in Proc. Nat. Acad. Sci. USA, vol. 100,
pp. 3870–3873, Apr. 2003.
[36] M. Lanza et al., “Grain boundaries as preferential sites for resistive Menelaos Tsigkourakos received the B.Sc.
switching in the HfO2 resistive random access memory structures,” Appl. degree in physics from the University of Athens,
Phys. Lett., vol. 100, no. 12, pp. 123508-1–123508-4, Mar. 2012. Athens, Greece, in 2007, the M.Sc. degree from
[37] O. Pirrotta et al., “Leakage current through the poly-crystalline HfO2 : the KTH Royal Institute of Technology, Stock-
Trap densities at grains and grain boundaries,” J. Appl. Phys., vol. 114, holm, Sweden, in 2010, and the Ph.D. degree
no. 13, pp. 134503-1–134503-5, Oct. 2013. from the University of Leuven, Leuven, Belgium,
[38] X. Cartoixà, R. Rurali, and J. Suñé, “Transport properties of oxy- in 2015.
gen vacancy filaments in metal/crystalline or amorphous HfO2 /metal He is currently a Post-Doctoral Researcher
structures,” Phys. Rev. B, Condens. Matter, vol. 86, no. 16, with the National Technical University of Athens,
pp. 165445-1–165445-5, Oct. 2012. Athens, focusing on the development of novel
[39] Z.-W. Wang, D.-J. Shu, M. Wang, and N.-B. Ming, “Diffusion of 2-D materials.
oxygen vacancies on a strained rutile TiO2 (110) surface,” Phys. Rev. B,
Condens. Matter, vol. 82, pp. 165309-1–165309-7, Oct. 2010.
[40] K. Kamiya et al., “Generalized mechanism of the resistance switch- Dimitris Tsoukalas received the Diploma
ing in binary-oxide-based resistive random-access memories,” Phys. degree in electrical and mechanical engineer-
Rev. B, Condens. Matter, vol. 87, pp. 155201-1–155201-5, Apr. 2013, ing from the National Technical University of
doi: 10.1103/PhysRevB.87.155201 Athens (NTUA), Athens, Greece, in 1979, and
[41] S. Kim, C. Du, P. Sheridan, W. Ma, S. H. Choi, and W. D. Lu, the Ph.D. and Habilitation degrees from INP
“Experimental demonstration of a second-order memristor and its ability Grenoble, Grenoble, France, in 1983 and 1994,
to biorealistically implement synaptic plasticity,” ACS Nano, vol. 15, respectively.
no. 3, pp. 2203–2211, Feb. 2015. He joined NTUA as a Professor, where he
[42] T. Chang, S. H. Jo, and W. Lu, “Short-term memory to long-term was a Research Scientist at NCSR “Demokritos”
memory transition in a nanoscale memristor,” ACS Nano, vol. 5, no. 9, untill 2002.
pp. 7669–7676, Aug. 2011.