Resistive memory multilayer structure with self-rectifying and forming free properties

along with their modification by adding a hafnium nanoparticle midlayer

Irini Michelakaki and Panagiotis BousoulasNikos MaragosNikos BoukosDimitris Tsoukalas

Citation: Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films 35, 021501 (2017); doi:
10.1116/1.4968204
View online: http://dx.doi.org/10.1116/1.4968204
View Table of Contents: http://avs.scitation.org/toc/jva/35/2
Published by the American Vacuum Society

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Resistive memory multilayer structure with self-rectifying and forming free
properties along with their modification by adding a hafnium nanoparticle
midlayer
Irini Michelakakia) and Panagiotis Bousoulas
Department of Applied Physics, National Technical University of Athens, 15780 Zografou, Greece
Nikos Maragos
Institute for Nuclear and Particles Physics, N.C.S.R. “Demokritos,” 15341 Aghia Paraskevi, Greece
Nikos Boukos
Institute of Nanoscience and Nanotechnology, N.C.S.R. “Demokritos,” 15341 Aghia Paraskevi, Greece
Dimitris Tsoukalas
Department of Applied Physics, National Technical University of Athens, 15780 Zografou, Greece
(Received 17 August 2016; accepted 8 November 2016; published 18 November 2016)
Despite the amount of work that has been produced using TiO2 to study its resistance dynamic
properties, the switching mechanism is not fully understood. In this context, the authors have
fabricated and investigated the switching mechanism of TiO2 based memristors with and without the
incorporation of crystalline hafnium nanoparticles. The resistive switching of the devices needs no
electroforming and is dictated by electrode/film interface modifications. The results indicate that the
dominant conduction mechanism is Schottky emission while in the case of hafnium nanoparticles
incorporation, a synthesis of which has not been reported before, conduction prevailing mechanism
changes to Fowler–Nordheim tunneling. Insight on device operation can be obtained by revealing the
role of nanoparticles on loss of rectifying properties, through local modification of oxygen vacancy
C 2016 American Vacuum Society. [http://dx.doi.org/10.1116/1.4968204]
concentration. V

I. INTRODUCTION nanoparticles has been already reported using chemical

Memristive devices are electrical resistance switches that
can retain a state of internal resistance based on the history of
applied voltage. The resistive switching observed in memris-
tive devices has attracted widespread attention in recent years
due to their potential application in next generation nonvolatile
memory technology. An important class of memristive devices
are oxide based resistive switches, which consist of a simple
metal/oxide/metal thin-film stack.1–3 Although various models
for explaining the resistive switching mechanism have been
proposed, the underlying physical mechanism remains still
unclear and this is an important drawback for the widespread
production of resistive memories.4,5 Among various oxides,
TiO2 is frequently and widely investigated as a standard mate-
rial due to its variety of functionalities, including unipolar,
bipolar, and threshold resistive switching.6–9 Another obstacle
toward industrial exploitation is the need of electroforming
process that seems unavoidable in some cases for proper
device operation.10
In this work, resistive memories consisting of TiO2 and
metal electrodes, in a metal-insulator-metal configuration of a
planar capacitor were fabricated. In order to investigate the
influence of nanocrystals incorporation in the bulk oxide,
crystalline hexagonal Hf nanoparticles (NPs) were embedded
within the TiO2 thin film. Hf NPs were grown by a gas con-
densation technique in vacuum that allows their incorporation
within the metal oxide film without vacuum breaking. We
remark that although the fabrication of hafnium oxide
a)
Electronic mail: michelakaki.irini@gmail.com
synthesis11,12 we have not identified any prior study demon-
strating the growth of hafnium nanoparticles but only compu-
tationally based approach to study their shape and size as a
function of growth temperature.13 There are several works
regarding the role of noble metal nanoparticles like Au, Pt,
and Ru in the resistive properties of various oxides and which
report an improvement in the device performance.14–16 In this
study, the Hf metallic nanoparticles used, in contrast with
noble metals, can interact with the surrounding oxygen rich
environment since they can be oxidized and consequently
modify the vacancy defect density in the oxide. In addition,
hafnium is fully compatible with semiconductor technology
since hafnium oxide is already used as gate dielectric in
advanced devices while noble metals are rather avoided.
Following a step of nanoparticle growth study, we have then
proceeded to two terminal device fabrication and measure-
ments to compare the operation of resistive switching with
and without the introduction of nanoparticles. We have
observed that the insertion of hafnium nanoparticles in the
TiO2 film induces an additional switching mechanism rather
than simply improving the device performance that we
explain through the increase of vacancy concentration and its
impact on electronic conduction mechanisms. Furthermore, in
both devices, no electroforming was necessary while it is
worth mentioning that the pristine sample without the nano-
particles shows excellent rectifying characteristics. This is
attributed to the Schottky barrier modification of TiO2 =Au
contact from oxygen vacancies while the presence of Hf nano-
particles notably modifies their distribution resulting in loss of
this effect as analyzed in the following text.

021501-1 J. Vac. Sci. Technol. A 35(2), Mar/Apr 2017 0734-2101/2017/35(2)/021501/9/$30.00 C 2016 American Vacuum Society
V 021501-1
021501-2 Michelakaki et al.: Resistive memory multilayer structure with self-rectifying and forming free properties 021501-2

pressure prior deposition was 1:2  106 mbar, the sputtering

FIG. 1. (Color online) Schematic illustration of the (a) Au=Ti=TiO2 =Au ref-
erence sample and (b) Au=Ti=TiO2 =Hf NPs=TiO2 =Au nanoparticles con-
taining sample. The inset shows a scanning electron microscopy image of
the nanoparticles containing sample without the Au electrodes. The textured
TiO2 surface is due to the underlying Hf nanoparticles.
power 200 W, and the argon and oxygen flow was 20 and 12
sccm, respectively. The Hf nanoparticles were produced by
an inert gas condensation method. A vapor of Hf atoms metal
was produced by dc sputtering of a high purity Hf target
(99.9%) in a high pressure Ar atmosphere. The high pressure
led to aggregation of the Hf atoms into particles, which were
forced due to a pressure difference to enter a deposition cham-
ber, where they landed softly on the TiO2 substrate (Fig. 2).
Transmission electron microscopy (TEM) and atomic force
microscopy (AFM) images revealed that the nanoparticles
have hexagonal shape, with size of 15  16 nm (height 
diameter) and surface density about 6  1010 cm2 (Fig. 3).
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.
Structural characterization of the TiO2 film and the Hf
nanoparticles was performed by grazing incidence x-ray
diffraction (GIXRD). An X’PERT Pro diffractometer was
employed for x-ray measurements. The instrument was

Memristors with self-rectifying characteristics are impor-

tant to overcome the sneak-path (leakage) current in cross-
point memory arrays. Crosspoint arrays offer high memory
density, but in order to obtain high sensitivity while reading
the array, the reverse leakage current has to be suppressed.17

II. MATERIAL GROWTH AND CHARACTERIZATION

The device fabrication process for both samples is based on
physical vapor deposition methods and is as follows. First the
bottom electrode was deposited by e-gun evaporation of a
4 nm Ti adhesion layer followed by a 40 nm Au layer on a
SiO2 substrate. Then, in the case of reference sample, a 44 nm
TiO2 layer was RF sputtered. In the case of the nanoparticles
containing sample, metallic Hf nanoparticles were sandwiched
between two 22 nm TiO2 RF sputtered layers. In Fig. 1, we
show a schematic illustration of the device structures.
The TiO2 sputtering conditions were identical for both
samples. The TiO2 deposition was carried out at room tem-
perature, and a high purity (99.9%) metallic Ti target was
used in the presence of oxygen reactive gas. The chamber

FIG. 3. (Color online) (a) Transmission electron microscopy image of the of

FIG. 2. (Color online) Schematic representation of principle of operation of
an inert gas operation technique.
the as deposited Hf nanoparticles with mean size of 15  16 nm (height
 diameter). The density of the nanoparticles embedded in the TiO2 bulk
corresponds to the density illustrated on the TEM image and is equal to
6  1010 cm2 . The inset shows a histogram with the diameter distribution.
(b) Atomic force microscopy image of Hf NPs. The height (15 nm) of the
nanoparticles was estimated from the AFM image where the diameter
(16 nm) was calculated from TEM images.

J. Vac. Sci. Technol. A, Vol. 35, No. 2, Mar/Apr 2017

021501-3 Michelakaki et al.: Resistive memory multilayer structure with self-rectifying and forming free properties
operated in a continuous scan mode in increments of
0:05 2h, and counts were accumulated for 10 s at each step.
The angle of incidence x was set to 0.5 . The x-ray patterns
are illustrated in Fig. 4. Concerning the hafnium nanopar-
ticles the x-ray patterns reveal that they have hexagonal
closed packed structure (HCP) with all peaks except of two
matching with the HCP hafnium structure [Fig. 4(a)]. This
finding is in agreement with previous studies for bulk haf-
nium18 as well as for hafnium deposited thin film19 that have
been both reported with the HCP structure. More recently,
computational studies of crystallization of hafnium nanopar-
ticles also reveal that Hf nanoparticles with diameter above
8 nm at low temperature crystallize at the HCP structure.13
The other two peaks are at 30.76 , 50.45 and fit with both,
orthorhombic HfO2 and Hf 7 N4 O8 . The most likely explana-
tion is that the outer shell of the nanoparticles is already oxi-
dized due to the naturally occurring reaction of hafnium
with oxygen when exposed to atmospheric air. Oxidation
confirming test experiments of Hf NPs were performed at
different temperatures (Tox ¼ 300; 450; 600  C) under oxy-
gen flow for 1 h. The x-ray patterns reveal that all observed
peaks at different temperature match with HfO2 [Fig. 4(c)].
Already at Tox ¼ 300  C, Hf peaks disappear, which could
signify that either the Hf nanoparticles are completely oxi-
dized to HfO2 or that they are partially oxidized to such
extent that the remaining Hf is not sufficient to give rise to
x-ray diffraction peak. The x-ray results demonstrate that
FIG. 4. (Color online) X ray pattern of (a) nanocrystalline hafnium nanopar-
ticles with hexagonal close packed (HCP) lattice (b) amorphous TiO2 thin
film. (c) X-ray patterns after oxidizing Hf nanoparticles at different tempera-
tures in vacuum under oxygen flow for 1 h. The observed peaks match all
with HfO2 . Hf peaks are not present. All x-ray patterns were recorded with
the GIXRD method.
JVST A - Vacuum, Surfaces, and Films
021501-3
Hf nanoparticles start to oxidize at low temperatures.
Concerning the TiO2 structure, the x-ray pattern reveals that
it has an amorphous structure [Fig. 4(b)].
III. ELECTRICAL CHARACTERIZATION
Electrical measurements were performed with an
HP4140B picoamperometer, while ns pulses were applied
with an HP8116A pulse generator. In all measurements, the
voltage was applied to the top Au=Ti electrode, and the bot-
tom 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, if not
stated otherwise, the measurements were performed on elec-
trode pads with lateral dimensions of 100  100 lm.
Figure 5 shows a typical current–voltage hysteresis curve
of the reference and NPs containing sample. Both devices
show uniform performance, as the I–V curves recorded at
many different memory cells exhibit similar hysteresis. The
nonzero current for the zero applied voltage observed in the
characteristic I–V of both devices implies that there is an
internal electric field possibly attributed to fixed charge
trapped in the device during fabrication. Concerning reference
sample, it shows hysteretic behavior with self-rectifying char-
acteristics. When a negative voltage sweep from 0 to 3:5 V
FIG. 5. (Color online) Current–Voltage (I–V) curves, at semilogarithmic
scale, of the devices operated in the memory switching mode: (a) reference
sample and (b) nanoparticles containing sample. The inset shows a sche-
matic representation of the proposed switching mechanism.
021501-4 Michelakaki et al.: Resistive memory multilayer structure with self-rectifying and forming free properties
is applied, the current starts to increase gradually at voltage
V  2 V, and the device is set from the high resistance state
(HRS) to low resistance state (LRS). When the voltage
becomes positive, the current stays low and the device resets to
the HRS. The resistance ratio is equal to Roff =Ron ¼ 103 at
V ¼ 1:5 V, and the rectification ratio for the HRS and LRS
measured at V ¼ 3 V is RHRS R ¼ 3  103 and RLRS R ¼ 2  104 ,
respectively.
Concerning the nanoparticles containing sample [Fig. 5(b)],
it shows hysteretic behavior with no obvious reset operation.
When a negative voltage sweep is applied from 0 to 4:5 V,
the current starts gradually to increase at voltage V  2 V,
and the device is switched from the HRS to LRS. Until this
point, the device behavior is similar to the reference sample. But
when the voltage becomes positive, no clear reset operation is
observed. During the positive voltage sweep from 0 to þ4:5 V,
a gradual increase in current is observed after V  þ2 V, and
the device seems to be set again to the LRS, but this time for
positive voltage. The resistance ratio is equal to Roff =Ron ¼ 103
at V ¼ þ2 V and Roff =Ron ¼ 102 at V ¼ 2 V. The device
does not show important rectification features.
In order to test the nonvolatile character of the samples,
the devices were also tested with voltage pulses (Fig. 6).
Voltage pulses which set and reset the sample were applied
consequently. After pulse application, the current readout fol-
lowed. The reference sample was set by a negative voltage
pulse Vset ¼ 3:5 V and reset by a positive voltage pulse
FIG. 6. (Color online) Response of (a) reference and (b) NPs containing sam-
ples on pulse applications. The samples were set and reset consequently by
voltage pulses followed by current readout. The last data on each figure
show the current retention of each sample 60 h after the set pulse application
at room temperature.
J. Vac. Sci. Technol. A, Vol. 35, No. 2, Mar/Apr 2017
021501-4
Vset ¼ þ3:5 V. The read voltage was Vread ¼ 1:5 V, and the
pulse duration tp ¼ 100 ns. NPs containing device was set by
positive voltage pulses Vset ¼ þ3:5 V and reset by negative
voltage pulses Vreset ¼ 6:5 V. The read voltage was
Vread ¼ þ2:5 V, and the pulse duration in this case was
tp ¼ 100 ns. The results indicate that both samples can be suc-
cessfully switched by voltage pulse application between the
two states of resistance and this certifies that the samples
work as nonvolatile memories. The Roff =Ron ratio is 102
and 5  102 for the reference and the NPs containing sam-
ple, respectively. Furthermore, satisfying current retention of
the LRS was observed for both samples after 60 h, at room
temperature.
IV. DISCUSSION AND MODELING
To understand the switching mechanism for both devices
(with and without NPs), the dependence of the resistance on
electrode area at HRS and LRS states was tested [Figs. 7(a)
and 7(b)]. The results show that the resistance is inversely
proportional to the electrode area at HRS and LRS. This
FIG. 7. (Color online) Dependence of resistance at HRS and LRS vs elec-
trode area for (a) reference sample and (b) NPs containing sample. The elec-
trode sizes were 100  100, 200  200, and 400  400 lm. Both devices
show dependence on the electrode area at both resistance states, HRS and
LRS.
021501-5 Michelakaki et al.: Resistive memory multilayer structure with self-rectifying and forming free properties 021501-5

scaling of device resistance with area is indicative that the

switching mechanism is rather of interface than of filamen-
tary type for both devices.20,21
Concerning first the reference device, the rectifying char-
acteristics and the dependence of the resistance on electrode
area, at both LRS and HRS states, reveal that the switching
mechanism is governed by the electrode/film interfaces.9,10,22
TiO2 is known as an n-type semiconductor because with oxy-
gen vacancies existing in TiO2 films being considered as
n-type dopants.23 Ti=TiO2 interface behaves as an ohmic con-
tact because Ti chemically reduces TiO2 to TiO2–x , creating a
significant increase in the concentration of oxygen vacancies
which reduces the electronic energy barrier at the Ti=TiO2
interface.24 On the other hand, the Au=TiO2 interface forms a
Schottky contact, because Au is chemically inert and it does
not induce oxygen vacancies at the TiO2 interface.24 The
device can then be considered as a Schottky diode (Au=TiO2
interface) in series with a resistance R, due to the bulk TiO2–x
and the ohmic contact (Fig. 5 inset). When the bias is positive,
this junction is reversely biased and small current is observed
at HRS [path 1, Fig. 5(a)], but when the bias becomes nega-
tive, the device is forward biased and the current increases
[path 2, Fig. 5(a)]. The I–V curve also shows a hysteretic
behavior because the device is switched to a LRS from HRS.
FIG. 8. (Color online) Fitting of J–V curves at LRS at negative bias of (a)
At LRS [paths 3 and 4, Fig. 5(a)], the device continues to reference sample (b) NPs containing sample with the Schottky emission
have rectifying characteristics. model assuming that the Schottky diode is connected with a series resis-
To shed light to the conduction mechanism, fitting of the tance. The black symbols correspond to the experimental values, and the red
line is the theoretical fitted curve. The experimental points not fitted in the
experimental data using different conduction models was
low voltage region correspond to a current due to an internal electric field,
performed. The I–V response of the LRS [Fig. 5(a)] is per- possibly attributed to charged species trapped in the oxide during
fectly fitted with the Schottky emission model [Fig. 8(a)] fabrication.
when it is assumed that the Schottky diode is connected with
a resistance in series [Eq. (1)].25 As can be seen in Fig. 5(a), affected strongly by the series resistance R ¼ V=I  2=106
the I–V curves are bent due to the current saturation effect ¼ 2 MX.
due to the series resistance. Similar deviation from the line- Furthermore, in order to test the validity of the Schottky
arity of the I–V plot, at semilogarithmic scale, due to series emission model in these samples, I–V measurements at dif-
resistance has been also observed by other groups26 ferent temperatures were recorded and fitted with the above
    mentioned conduction model. From the fitting results, it
qVD qðV  IRÞ seems that the theoretical curve fits well to the experimental
I ¼ Io exp ¼ Io exp with
nkT nkT results (Fig. 9). This agreement supports further the assump-
 
qUB tion that the conduction mechanism is governed by the
Io ¼ AA T2 exp ; (1) Schottky emission model that assumes the Schottky diode
kT
being connected in series with a resistance R.
where Io is the saturation current, n is the ideality factor, VD The fact that the LRS is governed by the Schottky emis-
is the voltage across the diode, V is the applied voltage, R is sion mechanism leads to the conclusion that the hysteresis
the series resistance which is associated with the bulk TiO2 loop is due to a modification of the Schottky barrier at the
and the ohmic contact, T is the absolute temperature, q is the Au=TiO2 interface. A reasonable physical scenario implies
electron charge, k is the Boltzmann constant, UB is the that when a negative voltage is applied, oxygen ions O2
Schottky barrier height, A is the effective diode area, and A move from the oxygen rich TiO2 region around the TiO2 =Au
is the effective Richardson constant for Au=TiO2 , assumed interface, to the positively biased anode (bottom Au
to be 1200 A cm2 K2 .27
From the fitting parameters, the Schottky barrier height TABLE I. Schottky diode parameters calculated from the fittings with the
UB , the ideality factor n, and the series resistance R were cal- Schottky emission model.
culated (Table I). Similar values for Schottky barrier height at
Au=TiO2 =Ti structure were derived by other groups.28 The Sample UB ðeVÞ N R ðXÞ
value of the series resistance is rational as it is close to the Au=TiO2 1.17 2.15 2:7  106
value of resistance estimated roughly at the saturation regime Au=TiO2 =Hf=TiO2 0.85 15.4 7  105
of the I–V curve [path 3, Fig. 5(a)] where the current is

JVST A - Vacuum, Surfaces, and Films

021501-6 Michelakaki et al.: Resistive memory multilayer structure with self-rectifying and forming free properties
FIG. 9. (Color online) Fitting of J–V curves at LRS at negative bias at different temperatures of (a) reference sample and (b) NPs containing sample with the
Schottky emission model, assuming that the Schottky diode is connected with a series resistance. The black symbols correspond to the experimental values,
and the red line is the theoretical fitted curve.
electrode) where they accumulate, leaving behind oxygen
vacancies V2þ o . This process results in an increase in the Vo
2þ
concentration at the TiO2 =Au interface, which dopes the
semiconductor, leading to a reduction of the Schottky barrier
width9 and the device is set to the LRS. When the voltage
becomes positive, oxygen ions O2 again get incorporated
into the TiO2 film, recombine with the oxygen vacancies
V2þo , and the Schottky barrier recovers to its initial state.
This explanation is further supported by observations of
other groups that report trapping of the oxygen ions at the
bottom electrode in the form of gas bubbles, which disappear
only when the voltage of the appropriate polarity is applied
and forces the oxygen to reenter into the oxide.10
Concerning then the device with Hf NPs, a hysteresis
loop is observed for both voltage polarities but the abnormal
characteristic is that the reset process seems to be missing
[Fig. 5(b)]. To explain this result, we first exclude the thresh-
old switching mode operation because the device is nonvola-
tile as it was confirmed by application of voltage pulses [Fig.
6(b)]. Furthermore, the dependence of both resistance states
HRS and LRS on the electrode area hints that the switching
event is due to interface phenomena rather than being
explained by filament formation argument, similarly with
the reference sample. Due to the interaction of Hf NPs with
J. Vac. Sci. Technol. A, Vol. 35, No. 2, Mar/Apr 2017
021501-6
O2 , it is assumed that the Hf nanoparticles significantly
enhance the concentration of oxygen vacancies V2þ o in the
TiO2 bulk, leading to the formation of substoichiometric
TiO2–x and HfO2–x in the area surrounding the nanoparticles.
This assumption is supported by the x-ray patterns [Figs.
4(a) and 4(c)]. Furthermore, the Ti=TiO2 and Au=TiO2 inter-
faces are correspondingly considered as Ohmic and Schottky
using the same arguments already presented in the case of
the reference sample. For these reasons, the nanoparticle
containing film can be then as well considered as a Schottky
diode (Au=TiO2 interface) in series with a resistance which
is expected in that case to be smaller than the series resis-
tance of the reference structure (without NPs).
When a negative applied voltage is applied, the NP and
reference samples operate similarly. Again the most likely
explanation for the observed switching phenomena at nega-
tive voltages is the modification of the Schottky barrier at
the Au=TiO2 interface. This assumption is justified by the fit
of the experimental data [path 3, Fig. 5(b)] with the Schottky
emission model when assumed that the Schottky diode is
connected with a series resistance [Eq. (1)]. The fitting
results are shown in Fig. 7(b) and the calculated parameters
in Table I. Both calculated parameters (series resistance and
Schottky barrier height) of the NPs containing sample are
021501-7 Michelakaki et al.: Resistive memory multilayer structure with self-rectifying and forming free properties
FIG. 10. (Color online) Temperature dependence of the resistance (R) used
as parameter in Schottky emission model [Eq. (1)].
smaller than that of the reference. This result confirms the
hypothesis that the Hf nanoparticles lead to the creation of
oxygen vacancies V2þ o in the TiO2 bulk that reduce the mate-
rial resistance and lower the barrier height. Finally, we
observe that the ideality factor is increased, which is a mani-
festation of a nonuniform barrier. In general, a high ideality
factor can arise from various factors such as thickness inho-
mogenities and imperfections of the diode.29 This appears
quite probable in the case of the NPs containing device, as
the existence of nanoparticles induces a nonuniform distribu-
tion of the oxygen vacancies in the bottom electrode
TiO2 =Au. Furthermore, in this case, I–V measurements were
performed at different temperatures and fitted with the
Schottky emission model. Also in this case, the fitting results
are satisfactory [Fig. 9(b)], confirming the assumption that
the most likely conduction model is Schottky emission.
Finally, from the fitting parameters at different temperatures
for both samples, the parameter resistance R is calculated.
The results confirm that there is an increase in the resistance
with decreasing temperature (Fig. 10) that is consistent with
the assumption that the series resistance is due to the semi-
conducting TiO2–x .
FIG. 11. (Color online) Fitting of J–V curve at LRS at positive bias of the
NPs containing sample with the Fowler–Nordheim conduction mechanism.
The black symbols correspond to the experimental values, and the red line is
the theoretical fitted curve.
JVST A - Vacuum, Surfaces, and Films
021501-7
The hysteretic loop for positive voltage application can-
not be attributed to the formation of a filament consisting of
oxygen vacancies, which is a common case for resistive
memories based on transition metal oxides like TiO2 .22 If a
filamentary type switching was in place, the resistance of the
LRS would be independent of the electrode area. We assume
then that for the NPs containing sample, the switching event
for positive bias [Fig. 5(b)] is dictated by the Au=TiO2
Schottky interface physics. To strengthen this assumption,
fits were performed in the case of LRS and positive voltage
[path 1, Fig. 5(b)]. The experimental data show perfect fit
with the Fowler–Nordheim conduction mechanism [Eq. (2),
Fig. 11]30
 
B
J ¼ AE2 exp  ; (2)
E
where A ¼ mq3 =m 8phUB and B ¼ 8p=3ð2m =h2 Þ1=2
ðU3=2
B
=qÞ, where E, UB , m, m , q, h are the electric field, bar-
rier height at injection electrode, electron mass, effective
electron mass, electron charge, and Planck’s constant,
respectively.
Although the Schottky diode at the Au=TiO2 is reversely
biased at positive voltage, a high leakage current is passing
through the device. The fitting results reveal that there is
electron transport from the metallic Au to the semiconduct-
ing TiO2 layer via tunneling. Under positive bias, oxygen
vacancies drift V2þ o toward the cathode (bottom electrode),
and there is a significant increase in oxygen vacancies con-
centration in the oxygen rich TiO2 region. Due to the drift of
the V2þ
o toward the TiO2 =Au interface, the increased concen-
tration of V2þ o leads to a decrease in the Schottky barrier
width,psince
ffiffiffiffiffiffiffiffiffi 31this depends on the doping concentration as:
w  1=N. At the same time, the electric field is also
locally enhanced due to the presence of the hexagonal Hf
nanoparticles. Thus, we support that electrons tunnel through
the thinned Schottky barrier, which manifests itself in the
F-N fit. This assumption is in fully accordance with other
groups’ data.32,33 From the I–V curve [Fig. 5(b)], it is
observed that the junction breakdown is reversible, because
when the voltage polarity becomes negative, oxygen vacan-
cies are repelled from the bottom electrode and the diode
recovers. Fitting with Fowler–Nordheim tunneling model
was then carried out at I–V recorded at different tempera-
tures (Fig. 12). The fitting results are satisfactory and sup-
porting the assumption that the LRS at positive voltages is
governed by Fowler–Nordheim tunneling.
The existence of nanoparticles in the film suggests how-
ever that barrier modification could also be attributed to their
charging. It is known from research in nanocrystal memories
which exhibit a flashlike operation that metallic or semicon-
ducting nanoparticles act as charge trap centers giving rise to
a memory window.34 Several research groups have also
investigated the influence of nanoparticles on resistive
switching using organic materials as the host matrix35 and
concluded that nanoparticles can act as trapping centers
although no direct evidence about their charging was
brought. Charges in the insulator do have an influence on the
021501-8 Michelakaki et al.: Resistive memory multilayer structure with self-rectifying and forming free properties 021501-8

which allowed tunneling through the thinned reversely biased

TiO2 =Au Schottky barrier as it was confirmed by fitting the
experimental data of the NPs containing sample with
Fowler–Nordheim tunneling mechanism. The nonvolatile
character of both samples was demonstrated by switching the
material between HRS and LRS with appropriate low voltage
and short duration pulses followed by retention measure-
ments. Last but not least, we remark that the synthesis and
application of hafnium nanoparticles has not been previously
reported in the literature.

ACKNOWLEDGMENTS
The authors would like to acknowledge the financial
support from research program “Aristeia II” (Grant No.
4543). This research has been cofinanced by the European
Union (European Social Fund ESF) and Greek national funds
through the Operational Program “Education and Lifelong
Learning” of the National Strategic Ref. Framework (NSRF).
1
R. Waser and M. Aono, Nat. Mater. 6, 833 (2007).
2
D. S. Jeong, R. Thomas, R. S. Katiyar, J. F. Scott, H. Kohlstedt, A.
Petraru, and C. S. Hwang, Rep. Prog. Phys. 75, 076502 (2012).
3
J. J. Yang, D. B. Strukov, and D. R. Stewart, Nat. Nanotechnol. 8, 13
(2013).
4
K. Szot, M. Rogala, W. Speier, Z. Klusek, A. Besmehn, and R. Waser,
Nanotechnology 22, 254001 (2011).
5
H. S. Philip Wong and S. Salahuddin, Nat. Nanotechnol. 10, 191 (2015).
6
D. S. Jeong, H. Schroeder, and R. Waser, Electrochem. Solid State 10,
G51 (2007).
FIG. 12. (Color online) Fitting of J–V curve at LRS for V > 0 at different 7
P. Bousoulas, I. Michelakaki, and D. Tsoukalas, Thin Solid Films 571, 23
temperatures of the NPs containing sample with the Fowler–Nordheim con- (2014).
duction mechanism. The black symbols correspond to the experimental val- 8
Y. L. Huang, S. C. Chao, D. H. Lien, C. Y. Wen, J. H. He, and S. C. Lee,
ues, and the red line is the theoretical fitted curve. Sci. Rep. 6, 23945 (2016).
9
J. J. Yang, M. D. Pickett, X. Li, D. A. Ohlberg, D. R. Stewart, and R. S.
potential distribution and consequently can modify interface Williams, Nat. Nanotechnol. 3, 429 (2008).
10
J. J. Yang, F. Miao, M. D. Pickett, D. A. Ohlberg, D. R. Stewart, C. N.
barriers explaining the observed hysteretic I–V behavior as it Lau, and R. S. Williams, Nanotechnology 20, 215201 (2009).
11
has been proposed in the early work of Simmons and A. Ramadoss, K. Krishnamoorthy, and S. J. Kim, Mater. Lett. 75, 215
Verderber.36 12
(2012).
V. Jayaraman, G. Bhavesh, S. Chinnathambi, S. Ganesan, and P. Aruna,
To discern about the two mechanisms originating from Mater. Express 4, 375 (2014).
nanoparticle incorporation in the film which were discussed 13
S. Xiong, W. Qi, B. Huang, M. Wang, and L. Wei, J. Phys. Chem. C 115,
above more investigations will be needed including nanopar- 10365 (2011).
14
ticle density and size effects on memory performance. P. Bousoulas, S. Stathopoulos, D. Tsialoukis, and D. Tsoukalas, IEEE
Electron Device Lett. 37, 874 (2016).
15
J. H. Yoon et al., Adv. Mater. 25, 1987 (2013).
16
V. CONCLUSIONS M. Uenuma, B. Zheng, K. Kawano, M. Horita, Y. Ishikawa, I. Yamashita,
and Y. Uraoka, Appl. Phys. Lett. 100, 083105 (2012).
17
In this work, the switching mechanisms of Au=Ti=TiO2 Y. Gao, O. Kavehei, S. F. Al-Sarawi, D. C. Ranasinghe, and D. Abbott,
=Au and Au=Ti=TiO2 =Hf NPs=TiO2 =Au two-terminal devi- Integration 54, 56 (2016).
18
J. Trampenau, A. Heiming, W. Petry, M. Alba, C. Herzig, W. Miekeley,
ces were investigated. Both devices were electroforming free, and H. R. Schober, Phys. Rev. B 43, 10963 (1991).
but the reference sample (Au=Ti=TiO2 =Au) also showed 19
O. Jin and B. X. Liu, Mater. Lett. 27, 165 (1996).
20
remarkable self-rectifying characteristics. The switching A. Sawa, Mater. Today 11, 28 (2008).
21
D. Ielmini and R. Waser, Resistive Switching (Wiley-VHC, Hoboken, NJ,
mechanism was in both structures dictated by the film/bottom
2016), Chap. 16.
electrode (TiO2 =Au) interface Schottky barrier modification. 22
P. Bousoulas, J. Giannopoulos, K. Giannakopoulos, P. Dimitrakis, and D.
Fitting of the experimental results with various conduction Tsoukalas, Appl. Surf. Sci. 332, 55 (2015).
23
mechanisms reveals that for negative voltages both structures P. Kofstad, Nonstoichiometry, Diffusion, and Electrical Conductivity in
Binary Metal Oxides (Wiley Interscience, New York, 1972).
follow a Schottky emission mechanism, where the TiO2 =Au 24
J. J. Yang et al., Appl. Phys. A 102, 785 (2011).
Schottky junction is assumed connected with a series resis- 25
S. K. Cheung and N. W. Cheung, Appl. Phys. Lett. 49, 85 1986.
26
tance. However, the incorporation of Hf nanoparticles in the M. Ravinandan, P. K. Rao, and V. R. Reddy, Semicond. Sci. Technol. 24,
035004 (2009).
TiO2 bulk led to a strong increase in the leakage current for 27
H. Zhang, M. Zhang, C. Feng, W. Chen, C. Liu, J. Zhou, and S. Ruan,
positive voltages attributed to an increase in the oxygen Appl. Opt. 51, 894 (2012).
28
vacancies concentration and to electric field enhancement E. W. McFarland and J. Tang, Nature 421, 616 (2003).

J. Vac. Sci. Technol. A, Vol. 35, No. 2, Mar/Apr 2017

021501-9 Michelakaki et al.: Resistive memory multilayer structure with self-rectifying and forming free properties 021501-9

29 33
R. K. Gupta, K. Ghosh, and P. K. Kahol, Curr. Appl. Phys. 9, 933 (2009). T. Boles, L. Xia, A. Hanson, A. Kaleta, and C. McLean, “Reverse leakage
30
Y. L. Chiou, J. P. Gambino, and M. Mohammad, Solid State Electron. 45, current and breakdown voltage improvements in GaN Schottky diodes,” in
1787 (2001). CS Mantech Conference, Denver, CO, 9–22 May (2014).
31 34
S. M. Sze, Physics of Semiconductors, 2nd ed. (John Wiley & Sons, New D. Tsoukalas, P. Dimitrakis, S. Kolliopoulou, and P. Normand, Mater. Sci.
York, 1981). Eng., B 124–125, 93 (2005).
32 35
J. Aarik, V. Bichevin, I. Jogi, H. Kaambre, M. Laan, and V. Sammelselg, J. C. Scott and L. D. Bozano, Adv. Mater. 19, 1452 (2007).
36
Open Phys. 2, 147 (2004). J. G. Simmons and R. R. Verderber, Proc. Roy. Soc. A 301, 77 (1967).

JVST A - Vacuum, Surfaces, and Films