RESEARCH ARTICLE

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A Voltage-Driven Transport Model to Identify Ion Migration

as the Rate-Limiting Step in Memristive Switching
Jorge Luis Vazquez-Arce,* Joel Molina-Reyes, Oscar Edel Contreras, and Hugo Tiznado

ability to function both as memory and

The physics behind the switching kinetics of memristors is gradually resistors.[1] The basic structure com-
becoming clearer. The periods required for the onset of electromigration prises two parallel metal electrodes sep-
within memristors and the activation or deactivation of the low-resistance arated by a solid-state nanometer-thick
state—referred to as the incubation and switching times—exhibit electrolyte, with its operation involving
the application of voltage to switch be-
non-linearity with applied voltage. This behavior prevails depending on the tween low and high-resistance states.[2]
rate-limiting step comprising nucleation and filament growth, electron This process occurs due to the movement
transfer at the electrode/electrolyte interface, and ion migration through the of charged species, such as ions or vacan-
electrolyte. Herein, a model is introduced for ion migration as the rate-limiting cies within the memristor, that alter the
step. This model analyses the incubation time and analytically correlates it material’s conductivity and, therefore, its
resistance.
with the electric field, diffusion coefficient, and temperature, facilitating the
In the early years of the recent decade,
determination of threshold voltage and diffusivity from high to low resistance investigating the insights of switching
states for ion migration as the rate-limiting step. By exploring parallel plate mechanisms remained at the forefront
cells with Yttria-Stabilized Zirconia (YSZ) of nanometer thickness, the of research,[3] primarily due to the pro-
application of the model is illustrated and the fundamental equations are found impact of kinetics on the mem-
applied to outstanding memristive cells in the literature. The applicability of ristor’s operating window.[4] The analy-
sis complexity arises from the fact that
this model to cells of various charge carriers is proposed, ranging from the flux of charged species triggers in-
vacancies and electron transport to oxygen ions and metal cations, denoting ternal, interface, and migration reac-
its potential importance. tions, which are challenging to differen-
tiate and incorporate into a comprehen-
sive model of voltage-driven transport.[5,6]
1. Introduction The scientific community has categorized the mechanisms
based on the species and phenomena involved during the oper-
Since their discovery, memristors have emerged as crucial de- ation of the devices. Memristors that rely on the conduction of
vices in artificial neuromorphic systems, owing to their unique oxygen anions (O2 − ), metal cations (M+ ), and oxygen vacancies
(Ovac ) are commonly referred to as redox-based resistive switch-
ing random access memory (ReRAM).[7]
J. L. Vazquez-Arce On the other hand, if the operation involves the reversible elec-
Centro de Investigación Científica y de Educación Superior de Ensenada trochemical reduction and oxidation of metal ions, typically from
Ensenada, BC 22860, México a metal electrode, it is known as an electrochemical cell (ECM).[8]
E-mail: jorgevazquez@ens.cnyn.unam.mx
Another category is valence change memory (VCM), where the
J. L. Vazquez-Arce, O. E. Contreras, H. Tiznado
switching process is based on the change in oxidation states (va-
Centro de Nanociencias y Nanotecnología
Universidad Nacional Autónoma de México lence states) of specific cations within the solid-state material.[9]
Km 107 Carretera Tijuana-Ensenada s/n, Ensenada, BC 22860, México Thermochemical (TCM) mechanisms[10] represent another type,
J. Molina-Reyes wherein the memory cell relies on the flow of heat or ther-
Departamento de Electrónica mal conductivity to achieve the switching process. Additionally,
Instituto Nacional de astrofísica phase change memories (PCM)[11] form an additional classifica-
Óptica y Electrónica
Tonantzintla, Puebla 72 840, México tion where the cell operates based on the reversible phase change
of material between its amorphous and crystalline states.
The ORCID identification number(s) for the author(s) of this article Experimentally, researchers employ both direct and indirect
can be found under https://doi.org/10.1002/aelm.202300608 methods to characterize the transport mechanism in mem-
© 2023 The Authors. Advanced Electronic Materials published by ristors. Direct characterization involves in situ observation of
Wiley-VCH GmbH. This is an open access article under the terms of the the cell during its operating conditions. For instance, Yang
Creative Commons Attribution License, which permits use, distribution and coworkers investigated the activation of the memristive
and reproduction in any medium, provided the original work is properly
cited.
switching mechanism in an Ag/SiO2 /Pt ECM cell using trans-
mission electron microscopy (TEM).[12] By applying voltages
DOI: 10.1002/aelm.202300608

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ranging from 8 to 10 V, the low-resistance state (LRS) was ac-
tivated, and conversely, applying -10 V deactivated the LRS, re-
sulting in the high-resistance state (HRS). In the micrographs,
they directly observed the forming of a conductive path (fila-
ment) consisting of Ag cations during the LRS state and the
gradual fading of this filament when transitioning to the HRS
state.
Another direct observation was made by Park and
collaborators[13] in a Pt/SiO2 /Ta2 O5 /TaO2-x /Pt VCM cell. They
found that during the activation of the LRS state, there is a
predominant flow of oxygen vacancies in the direction of the
current flux and a formation of a metallic cluster of Ta. To
conduct their study, they employed advanced techniques such
as Annular Dark-Field Imaging by Scanning Transmission
Electron Microscope (HAADF-STEM) and Electron Energy Loss
Spectroscopy (EELS).
By utilizing direct observations, researchers can closely track
the reactions during the migration of charge carriers within the
memristor cells. However, it is worth noting that these cutting-
edge characterizations can be pretty costly, limiting their ac-
cessibility to only a few research groups with the necessary
resources.
Another equally essential approach to elucidate the memris-
tive mechanism is modeling the electrical response. It is worth
noting that the memristor, one of the fundamental elements in
electrical circuits along with resistor, capacitor, and inductor, can
be effectively modeled with its basic circuit equations.[2] How-
ever, the unique characteristics of the electrolyte and interfaces
at the nanoscale have required the development of more com-
prehensive models that encompass the underlying physics and
chemistry of the mechanism.[14]
In recent years, significant progress has been made in under-
standing the threshold potentials by modeling switching kinetics.
In this sense, the work by Menzel et al.[14] presents a compre-
hensive investigation of the models that allow prediction[15] and
distinguish[16] the contributions of three rate-limiting processes
in different voltage ranges: (I) Nucleation and growth of filaments
(analyzed through nucleation time and electron tunneling equa-
tions), (II) electron transfer during the reduction/oxidation of
ions at interfaces (using Butler-Volmer equations), and (III) ion
migration through the electrolyte toward interfaces (applying the
Mott-Gurney law for ion hopping). Those models facilitate the de-
termination of activation energies, transfer coefficients, and po-
tentials associated with each rate-limiting step at various voltage
levels.
Among the fundamental mechanisms of memristors, thresh-
old kinetics emerges as a critical aspect since it identifies the
minimum potential for the transition from the HRS state to the
LRS state.[7] Physically, before the threshold potential, a criti-
cal process takes place involving the accumulation or redistribu-
tion of charged species (O2 − , M+ , or Ovac ) to form the conduc-
tive filament. Before establishing this conductive filament, these
charged species, including electrons and holes, play a critical role
in the ongoing degradation of the electrolyte or metal oxide as
it is subjected to continuous electrical stress. Given the signif-
icance of the threshold potential in characterizing memristors,
it becomes crucial to establish a well-controlled characterization
setup. For example, in current-voltage curves, inadequately con-
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trolled voltage ramps (V/s) may lead to an inability to appreciate
the switching threshold accurately.
An alternative is the implementation of current-time curves
under constant voltage. In the previously mentioned research
work by Yang et al.,[12] they implemented current-time curves to
observe the formation of the conductive filament and observed a
unique phenomenon known as the “incubation time” during the
transition from the HRS state to the LRS state. This incubation
time refers to the duration required before the transition process
begins. Observation involves monitoring for an abrupt increase
in current after the incubation time has elapsed. Interestingly,
they also found that the duration of the incubation time is in-
versely dependent on both the applied voltage and the operating
temperature.
In the study conducted by Tsuruoka et al.,[17] it describes the in-
cubation time in current-time curves for ECM Cu/Ta2 O5(15 nm) /Pt
and Pt/Ta2 O5(15 nm) /Pt cells. The incubation time is character-
ized by a rapid and almost exponential decay in current over
a short time. After incubation time, the LRS state is activated,
and the current experiences a sudden and sharp increase until
it reaches a stable value, indicating the equilibrium in the LRS
state.
Building upon the existing knowledge, this study aims to in-
troduce a novel model for switching kinetics, focusing on ion
migration as the rate-limiting process. What sets this model
apart is its exploration of the incubation time, rather than the
switching time, as a critical parameter. The theoretical work
for this model was laid by R. Kirchheim,[18] who applied it to
voltage-driven transport phenomena like flash sintering[19] and
Al cation migration,[20] and in a recent study, the authors of this
work demonstrated the model experimentally for oxygen vacancy
electromigration.[21] The model accurately determines the rate-
limiting diffusion coefficient and threshold voltage, establishing
a relationship between the incubation time, temperature, and ap-
plied electric field.
To demonstrate the model’s general applicability, we employed
a specific cell based on Yttria-Stabilized Zirconia electrolytes
(YSZ). YSZ’s history in solid-state applications, owing to its ex-
ceptional oxygen ion conductivity, holds promise for YSZ-based
memristors.[22–24] YSZ naturally contains a high concentration
of oxygen vacancies, which can be precisely controlled by vary-
ing the fraction of yttria into the Zirconia lattice. The num-
ber of oxygen vacancies is approximately half that of Y atoms,
ensuring a stable and controllable vacancy concentration. This
unique property allows YSZ electrolytes to be customized with
desired yttria concentrations for memristors. Also, the compati-
bility of YSZ to a CMOS (complementary metal-oxide semicon-
ductor) process enables its introduction into several processing
stages of an integrated circuit, thus paving the way for enhanc-
ing the functionality of advanced integrated logic and memory
technologies.
The cell configuration was Ru/YSZ(100 nm) /Au , operated at
temperatures ranging from 100°C to 170°C. It is explored the im-
plications of the model on the characteristic pinched hysteresis
loop observed in current-voltage curves and compared the appli-
cation of the model to other memristive cells reported in the lit-
erature, showcasing its versatility and ability to provide valuable
insights into various memristor devices.
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Figure 1. Schematic of the experiment for activating the memristive mechanism in Ru/YSZ(100 nm) /Au cell. a) Voltage signal applied over time. b)
Response current during the applied constant voltage. The log-log plot is shown in the inset. c) Current characteristics by applying the voltage sweep
cycles. The curves were taken at 140 °C with a constant voltage of 4 V. The superimposed voltage sweep was from −5 to 5 V.

2. Results the characteristic pinched loop in the current curve, commonly

studied in the switching mechanism, is observed (Figure 1c). It
2.1. Activating the Switching Mechanism is important to note that the switching hysteresis is not observed
when the voltage sweep cycles are applied at times shorter than
2.1.1. Describing the Electrical Setup and Response Characteristics the 𝜏 incubation .

To illustrate the model’s features for investigating the switch-

ing mechanism, we employed a constant voltage signal over
2.1.2. Insights into Ion Migration as Rate-Limiting in YSZ Electrolyte
time and conducted superimposed voltage sweeps using the ini-
tial constant voltage as a reference while monitoring the cur-
In recent years, voltage-driven transport in solid electrolytes has
rent (Figure 1a). After applying the constant voltage, the current
gained significant relevance, especially with the emergence of
showed a decay during the first few seconds due to the internal
memristors and phenomena like flash sintering[25] , which share
bias of the YSZ trapping electron carriers in a purely capacitive
essential transport characteristics. Flash sintering is a novel tech-
process (Figure 1b). This process involved charge accumulation
nology used for low-temperature densification of ceramic ma-
mediated by Ovac and O2 − at adjacent electrodes, putting the cell
terials, accomplished by applying an intense electric field to a
in a HRS state. Then, the current reached a minimum value, in-
metal/ceramic/metal cell at a specific temperature. During this
dicating the attainment of the maximum electronic conductivity
process, the electromigration of O2 − , M+ , or Ovac occurs, leading
in YSZ, and remained constant until it increased sharply due to
to an experimental observation of an abrupt increase in current
the onset of ionic conductivity (migration of Ovac ). We will refer to
that eventually stabilizes at a stationary value, similar to what is
the period until the onset of migration as the “incubation time”
observed in memristors. However, it is worth noting that flash
(𝜏 incubation ). A representative example of graphically determining
sintering is an irreversible process, whereas the transition from
the 𝜏 incubation is provided in Figure 1b. During the abrupt increase
the HRS to the LRS state in memristors is reversible. Despite this
in current, the growth rate remains constant. This section of the
difference, if ion migration through the electrolyte is the rate-
current curve allows for applying linear regression toward its ini-
limiting step in both phenomena, memristive and flash sinter-
tial minimum. The resulting X-axis value at the intercept gives
ing, they can be described using the theoretical model proposed
us the value of 𝜏 incubation .
by R. Kirchheim, where the ion motion is considered to be driven
As mentioned, the sharp increase in current marks the begin-
by joule heating and intense electric fields [18,19] . The validity of
ning of carrier migration from one electrode to the other through
this model has been demonstrated through theoretical and exper-
a purely conductive filament. As migration proceeds, the current
imental studies on the electromigration of aluminum cations in
reaches a maximum value, indicating the equilibrium of the mi-
metals [20] and oxygen vacancies in YSZ[21] . The model includes
gration reaction. This point corresponds to the “steady state,” rep-
an equation that correlates the observed 𝜏 incubation in the current
resenting the LRS state. The time taken to transition from the
curves and the applied electric field, as follows:
HRS state to the LRS state at a specific constant voltage is defined
as the “switching time.”
Once the steady state is achieved, we applied voltage sweep ( )2
1 RTl
cycles superimposed on the initial constant voltage. At this stage, Di = (1)
𝜏incubation FU

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Figure 2. a) 3D current curve as a function of time at different applied voltages to the cell Ru/YSZ(100 nm) /Au at 120 °C. b) Plot of the Uapplied versus the
square root of the inverse of the 𝜏 incubation .
In this equation, Di is the diffusion coefficient, R is the ideal
gas constant, T is the temperature, l is the thickness of the elec-
trolyte, F is the Faraday constant, and U is the applied voltage.
To illustrate it Figure 2a illustrates the 3D current curve of
the Ru/YSZ(100 nm) /Au cell at 120 °C, displaying different voltages
ranging from 3 to 5.25 V. The 𝜏 incubation , decreases as the applied
voltage increases. Concurrently, the current in the LRS state also
increases.
One notable feature of the model is the capability to calculate
the threshold voltage necessary for the onset electromigration.
In Figure 2a, when applying a voltage of 3 V, the current curve
remains purely capacitive for up to 300 s. Graphically, it is chal-
lenging to determine if the transition from the HRS state to the
LRS state will occur over a longer time. By rearranging Equation 1
in the following manner:
1 √ FU
√ = Di
𝜏incubation RTl
where is found that the applied voltage, Uapplied , is proportional to
the square root of the reciprocal of the incubation time, √1𝜏 . In
1
Figure 2b, it is shown the plot of Uapplied versus √
𝜏
using the cur-
rent data from Figure 2a. Extrapolating a straight line to the Y-axis
intercept can obtain the minimum voltage required to transition
from the HRS state to the LRS state (onset of migration). The
determined value is approximately 2.4 ± 0.19 V. Based on the fit-
ting, we can also determine that the 𝜏 incubation when applying 3 V
is ≈1210 s.
Figure 3a–d presents a schematic of the electromigration pro-
cess within the Ru/YSZ(100 nm) /Au cell. Upon applying the volt-
age during the HRS state, an accumulation of vö occurs at the Ru
negative electrode, along with e− at Au, the positive electrode. Ad-
ditionally, O2 − migrates from the Ru/YSZ interface and accumu-
lates at the Au/YSZ interface, resembling a redox reaction phe-
nomenon (previous research[21,26] has provided evidence of the
redox reactions at Au and Ru metal electrodes by physicochemi-
cal characterization). As the incubation time elapses, vö starts to
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react at the Ru negative electrode as described by the following
equation:
′
vö + ZrZr → vȯ + ZrZr
x
(3)
The metallic Zr atom receives an extra electron due to the mi-
gration of O2 − , leading to the formation of a Ru-Zr alloy. Once vȯ
are formed, they are transported to the positive electrode. At the
Au electrode, vȯ release their electrons:
vȯ → vö + e′ (4)
and this leads to a flux of vö in the opposite direction, maintain-
ing charge neutrality. The equilibrium of this reaction is observed
in the steady state, and as mentioned earlier, the diffusion coef-
ficient Di calculated by Equation 1 represents the rate-limiting
step.
This migration reaction leads to the formation of three distinct
(2)
internal regions within the YSZ: one where vȯ are generated, re-
sulting in predominant n-type conduction; another where vö are
formed, leading to dominant p-type conduction and an interme-
diate transport i-region between these two regions. The resulting
internal structure is analogous to p-i-n junctions.
An alternative way to verify the ionic conductivity is by revers-
ing the direction of the electrical circuit and assessing the voltage
drop (discharge) at constant current (Figure 3e). The discharging
voltage curves were obtained for each applied voltage in Figure 2a
at 2.2 μA cm−2 . The discharging voltage indicates the relaxation
of the p-i-n regions,[27] and the plateau shape indicates the trans-
port of ionic carriers, specifically O2 − in this case.
2.1.3. Incubation Time in Outstanding Literature on Resistive
Switching
In resistive switching, recent observations have highlighted the
significance of analyzing current-time curves for discerning the
threshold kinetics. In this section, some of them will be an-
alyzed. Messerschmitt et al.[28] conducted a study on a VCM
Pt/SrTiO3-𝛿(600 nm) /Pt cell, where they explored the activating of
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Figure 3. a–d) Schematic of the internal reaction during the electromigration process in the switching mechanism of the Ru/YSZ(100 nm) /Au cell. e)
Relaxation voltage at a constant current of 2.2 μA cm−2 after turning off the applied voltage at 120 °C.
the LRS state in current-time curves by applying constant volt-
ages ranging from 1 V to 4 V. They obtained current curves sim-
ilar to those shown in Figure 2a, and the incubation times from
their study are presented in Figure 4a. Another work by Tsu-
ruoka et al.[17] focused on the relationship between the threshold
voltage and the incubation time in an ECM Cu/Ta2 O5(15 nm) /Pt.
Figure 4a also includes incubation times for this cell, acquired
by applying voltages between 2.5 and 5 V. Additionally, the incu-
bation times from Buh et al.,[29] where they conducted a study
on a Pt/NiO(40 nm) /Pt cell, are also displayed in Figure 4a. Fi-
nally, the incubation times reported by Yang et al.[12] in an ECM
Ag/SiO2(200 nm) /Pt cell at high applied voltages of 10 and 26 V are
also included.
To determine the threshold voltage for each cell, we employed
the Ufield versus √1𝜏 plot introduced in Equation 2. Since the cells
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have different electrolyte thicknesses, we represented the ap-
plied voltage as the electric field. The results are illustrated in
Figure 4b, where the linearity of the graph validates the model’s
applicability to these cells. Extrapolating the graph toward the in-
tercept with the Y-axis at 0 enables us to find the threshold volt-
age. For the Cu/Ta2 O5(15 nm) /Pt cell,[17] the threshold voltage was
determined to be 1.90 V, with an incubation time of ≈5750 s
when applying 2 V. For the Pt/NiO(40 nm) /Pt cell,[29] the thresh-
old voltage was found to be 2.98 V, with a maximum incubation
time of ≈1600 s when applying 3 V. The Pt/SrTiO3-𝛿(600 nm) /Pt
cell[28] displayed a calculated threshold voltage of 0.78 V, while
the authors observed a threshold voltage of 1.2 V for activating the
LRS state. The slight discrepancy may be attributed to the dimin-
ishing changes in measured current near the threshold voltage,
making distinguishing more challenging. For the Yang cell,[12]
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Figure 4. a) A comparison of the incubation time for activating the switching mechanism in different memristive cells. b) Ufield versus
determination of the threshold voltage. c) Calculated diffusion coefficients using slopes from Figure 4b and Equation 5.
Ag/SiO2(200 nm) /Pt, the threshold voltage was determined to be
16.37 V.
Figure 4c shows the diffusion coefficients for all cells, calcu-
lated using the slopes from Figure 4b. According to Equation 2,
the slope of the Ufield versus √1𝜏 plot is approximately equal to:
√ F
m = Di
RT
The diffusion coefficient for the VCM Pt/SrTiO3-𝛿(600 nm) /Pt
cell[28] was determined to be 2.19 × 10−14 cm−2 s−1 , consis-
tent with values reported in the literature on oxygen vacan-
cies diffusion in SrTiO3 .[30] For the ECM Cu/Ta2 O5(15 nm) /Pt
cell,[17] the calculated diffusivity is 1.94 × 10−18 cm−2 s−1 , with
a magnitude similar to that measured by ion mass spectroscopy
for nano-thick Ta2 O5 .[31] The Pt/NiO(40 nm) /Pt cell[29] displayed
a diffusion constant of 4.84 × 10−16 cm−2 s−1 . For the ECM
Ag/SiO2(200 nm) /Pt cell,[12] the diffusion coefficient values ranged
between 7.54 × 10−17 cm−2 s−1 , closely resembling the values re-
ported for diffusing silver clusters through metallic surfaces.[32]
Our Ru/YSZ(100 nm) /Au cell exhibited a diffusion coefficient of
2.38 × 10−16 cm−2 s−1 .
To comprehend the model’s applicability to various voltage-
driven species migration systems, it is essential to understand
its fundamental premise. Under the influence of an electric field,
species undergo electromigration from one electrode to another,
resulting in species concentration changes over time. Whether
surpassing or falling below specific thresholds, these concen-
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1
√ plot for the
𝜏
tration shifts and trigger reactions propel the transport process.
For the specific case of YSZ and the migration of oxygen vacan-
cies and/or oxygen ions, previous research has extensively doc-
umented the boundaries and solutions of the model.[18,19,21] The
model enables the determination of critical parameters like the
unwanted electronic current maxima, the charge associated with
vacancies (single or double ionized), and oxygen ions. It also of-
(5) fers insights into the thickness of the migration region. Solutions
related to the transport of Al cations can be found in reference.[20]
On the other hand, potential challenges for this model arise when
considering ultra-thin electrolytes, so that electronic conduction
is now predominant, and the role of ion migration, along with the
diffusion properties of the ionic species of interest, could lead to
under or overestimations of the incubation time.
2.1.4. Exploring Rate-Limiting Ion Migration in Fast Memristive Cells
This section delves into fast-switching cells where incubation
times are in the ms-μs range. In these fast-switching cells, the in-
cubation time closely approximates the switching time, enabling
a direct analysis of threshold kinetics via Equation 1.
Recent studies in modeling memristors have led to a focused
analysis of the relationship between switching time and applied
voltage.[15,33,34] Researchers have identified distinct regions on
the switching time versus voltage curve, each associated with
intrinsic rate-limiting processes. In scenarios where the curve
exhibits a pronounced slope, the rate-limiting step pertains to
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1
Figure 5. a) Comparison of switching times from diverse, fast memristive cells. b–e) Ufield versus √ plots for threshold voltage determination.
𝜏

the nucleation and growth of the conduction filament. This phe- 1

nomenon is investigated using nucleation time and electron tun-
neling equations. In cases of medium slopes, the electron trans-
fer during the redox reactions of ions at interfaces governs the
rate-limiting process. Such instances are analyzed by the applica-
tion of Butler-Volmer equations. Soft slopes signify ion migration
as the rate-limiting process, and its behavior aligns with the prin-
ciples of the Mott-Gurney law for ion hopping. These approaches
facilitate the determination of activation energies, transfer coeffi-
cients, and overpotentials that influence the migration reaction.
Figure 5a provides switching time versus voltage curves, fea-
turing data extracted from various research papers that under-
score ion migration as the rate-limiting step within a specific
range of operating voltages. This compilation includes ECM cells
based on the migration of Ag cations[15,33–36] and a VCM cell in-
volving oxygen vacancy migration.[37]
In Figure 5b–e, we present Ufield versus √
𝜏
plots derived from
the data in Figure 5a. Given the substantial variation in Y-axis
values, the data was distributed across four distinct graphs. Once
again, the linearity observed in these Ufield versus √1𝜏 plots rein-
force the model’s validity within this specific range of operating
voltages. Our analysis culminates in extracting the diffusion co-
efficient and threshold voltage of this behavior, as summarized
in Table 1. Among the various cells, SiO2 is a prominent elec-
trolyte choice for facilitating Ag cation migration. Despite utiliz-
ing closely comparable thicknesses, disparities in threshold po-
tentials and diffusion coefficients highlight the critical role be-
tween counter-electrodes and SiO2 stoichiometry.
In the context of designing high-speed memristor devices,
identifying the rate-limiting step of the migration reaction
is essential for several reasons. Understanding what specific

Table 1. The calculated diffusion coefficient and the threshold voltage from the cells in Figure 5.

Cell Threshold voltage [V] Diffusion coefficient [cm2 s−1 ] Reference

LaNiO3 /LaFeO3(20 nm) /LaNiO3 4.84 4.22 × 10−10 [37]

Ag/HfO2(3 nm) /Pt 0.67 1.62 × 10−10 [15]
Ag/Ag:SiO2(10 nm) /Pt 0.22 1.21 × 10−13 [35]
Ag/SiO2(30 nm) /Pt 1.59 3.76 × 10−10 [36]
Ag/SiOx(5 nm) /graphite 1.91 3.04 × 10−12 [34]
Ag/SiO2(10 nm) /Pt 1.37 4.43 × 10−13 [33]
Ag/SiO2(10 nm) /IrO 1.33 1.03 × 10−11 [33]
Ag/SiO2(10 nm) /TiN 1.24 3.38 × 10−13 [33]
Ag/SiO2(10 nm) /Ru 0.36 2.74 × 10−11 [33]

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Figure 6. a) Current-time curves under a constant 3 V at temperatures between 120 and 170 °C. b) Comparative analysis of calculated diffusion coeffi-
cients. Data from McBrayer et al.[38] for the diffusion of Ag+ cations in SiO2 , is also included. c) Comparative of effective conductivity in the LRS state
at equilibrium.
process limits the migration reaction allows the optimization of
memristor design and materials. For example, if ion migration
through the electrolyte is identified as the limiting factor using
this model, researchers can focus on developing materials with
improved ionic conductivity while also studying the systematic
scaling down of their physical thickness. This could involve opti-
mizing electrolyte composition, crystal structure, or defect den-
sity to enhance ion mobility and reduce resistance during mi-
gration. Alternatively, and more generally, identifying the limit-
ing step in the pace of the migratory reaction allows us to focus
our efforts. If electron transfer at interfaces or nucleation and
growth are identified as limiting factors, optimization of elec-
trode materials or engineering of interfaces can be pursued to
minimize resistance, promote faster filament formation, and ac-
celerate switching. Therefore, by considering ion-migration for
even thinner YSZ materials, our model could deliver not only dif-
fusion coefficients and threshold voltages for switching but also
provide helpful parameters related to the operating conditions of
memristive devices like power consumption, switching velocities
and additional reliability parameters that are pretty important for
scaled-down devices in advanced technology nodes.
2.1.5. Temperature Dependence of the Incubation Time
Figure 6a depicts the current versus time curves of the
Ru/YSZ(100 nm) /Au cell under a constant 3 V across tempera-
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tures ranging from 120 to 170 °C. By employing Equation 1, the
diffusion coefficient was calculated, and its corresponding Ar-
rhenius plot is illustrated in Figure 6b. It is important to note
that in this scenario, we must account for U is equal to the
Uapplied − Uthreshold ,[21] which leads to a modified equation:
( )2
1 RTl
Di = ( ) (6)
𝜏incubation F Uapplied − Uthreshold
Within this analysis, the activation energy Ea, is ≈1.10 eV,
corresponding to the ionic conductivity in the YSZ.[39] The
data collected under 4 V from our previous work[21] is also in-
corporated, and the alignment between diffusion coefficients
across various voltages agrees with the model’s predictions,
wherein the motion of a planar front is the determinant
of velocity. In instances where diffusion governs the rate-
limiting step, the applied voltage does not affect the Di itself.
Instead, the variation in current and 𝜏 incubation pertains to the
increase of mobile charge carriers. Extrapolation of these dif-
fusion coefficients to elevated temperatures show congruence
between our values and those obtained through Secondary-
ion mass spectrometry measurements[39] in YSZ with varied
stoichiometry.
In the context of the Ag/SiO2 /Pt cell by Yang et al.,[12] the rela-
tionship between incubation time and temperature was explored
by employing the analysis of Equation 6. In Figure 6a, the
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Figure 7. a) Voltage signals employed for investigating the switching mechanism in the Ru/YSZ(100 nm) /Au cell. The experimentation occurred at 140 °C,
utilizing constant voltages between 0 and 4 V and a voltage sweep of ±5 V at 30 Hz. b) Distinctive current response during the experimental procedure.
c–f) A phenomenological model for the memristive hysteresis loop for the Ru/YSZ(100 nm) /Au cell, attributed to the internal p-i-n junction within the
YSZ. The behavior of its i-region and redox reactions is influenced by both voltage and frequency. Panels (c) and (d) replicate previous Figure 3a–d. The
impact of the superimposed voltage sweep becomes evident in panels (e) and (f), wherein this additional voltage input directly modulates the i-region.

calculated diffusion coefficient for Ag+ ions transported
through the SiO2 electrolyte revealed an activation energy of
0.35 eV.
Another aspect within the curves presented in Figure 6a is the
behavior of the steady-state current over long times (LRS state). It
is observed that as the temperature increases, the current reaches
higher values. These observations can be examined by the effec-
tive conductivity, with the expression:
ing voltages. In the context of this model, operating at higher
voltages increased the concentration of charge carriers, facili-
tating their movement and leading to a decrease in activation
energy.
2.2. Analysis of the LRS State Using Voltage Sweeps

isteady state 2.2.1. The Impact of Constant Voltage Offset

L
𝜎eff . =
Uapplied − Uthreshold A
where isteady − state is derived from current curves at long
times and AL represents the sample volume factor. Figure 6c
shows the evolution of 𝜎 eff. for the Ru/YSZ100nm /Au and
Pt/SrTiO3-𝛿(600 nm) /Pt[28] cells under different operating voltages.
The activation energy for the Ru/YSZ100nm /Au cell decreased
from 1.4 eV (at 3 V) to 0.67 eV (at 4 V). This change in conductivity
and activation energy can be attributed to the higher concentra-
tion of charge carriers within the conductive filament at higher
voltages.
Interestingly, our findings are consistent with those obtained
in the Pt/SrTiO3-𝛿(600 nm) /Pt cell.[28] Their exploration of effective
conductivity within the LRS state under varying applied voltages
shows a similar decrease in activation energy at higher operat-
(7)
The second phase of the experiment, as outlined in Section 2.1.1,
involves the application of superimposed voltage sweeps during
the stable LRS state. By visualizing Figure 7a, these superim-
posed voltage signals were conducted with the initial constant
voltage ranging from 0 to 4 V at 140 °C. The subsequent voltage
sweep was ± 5 V, operating at 30 Hz.
The response currents, as shown in Figure 7b, reveal a cor-
relation with the initial constant voltage. When the initial con-
stant voltage remains below 2 V, the current remains mainly flat,
aligned with the anticipated behavior of a polarizable capacitor
(HRS state).
In contrast, when the initial constant voltage surpasses the
2 V threshold, the pinched hysteresis loop characteristic of the
switching mechanism emerges. The current curve observed dur-
ing the transition from the HRS to the LRS state resembles that

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Figure 8. a–d) Variation in the current response for the Ru/YSZ(100 nm) /Au cell under superimposed ±5 V sweeps at 140 °C as a function of frequency.
The initial constant voltage was set to 4 V. e) Relationship between series voltage and frequency calculated using Equation 8. f) Set-current of HRS and
LRS states plotted against series resistance. g) Frequency-dependent variations in HRS and LRS resistances. Forward and reverse resistances measured
above 100 Hz are also included. Operational Regimes and Circuit Model of Ru/YSZ(100 nm) /Au Cell. h) Conductive filament development (dotted line)
with frequency-dependent i-region and Au oxidation. i) Desynchronization of conductive filament, i-region, and Au oxidation with increasing frequency.
j) Absence of conductive filament, coupled with reduced reactive capacitance at high frequency, enhances charge trapping. k) Proposed electrical model
for the Ru/YSZ(100 nm) /Au cell, illustrating parasitic resistances and components.

of a p-i-n diode, showing a soft transition near the threshold
voltage.
Considering the p-i-n regions formed within the
Ru/YSZ(100 nm) /Au cell, as discussed in Section 2.1.2, the
observed behavior can be illustrated as follows: Figure 7c–f illus-
trates the stages and their phenomena for the Ru/YSZ(100 nm) /Au
cell behavior based on internal p-i-n junction, which governs
the current-voltage characteristics depicted in Figure 7b. Of
particular significance is the presence of two serial resistances:
Rsi , associated with the resistance of the i-region, and Rsox , to
the redox process at the electrodes. Rsi , Rsox, as well as the ion
migration (O2 − , vȮ , and vÖ ) and redox reactions all depend on
the applied voltage and frequency. These phenomena exhibit
limitations in tracking their corresponding frequency-induced
variations at higher frequencies, a topic we will investigate later.
2.2.2. Voltage Sweeps Frequency and Multilevel Switching
Figure 8 shows current curves corresponding to ±5 V sweeps
at frequencies ranging from 5 Hz to 100 kHz for the
Ru/YSZ(100 nm) /Au cell at 140 °C. At frequencies below 50 Hz, an
apparent decrease of the applied voltage and current is observed
as frequency increases, as illustrated in Figure 8a,b.
The apparent decrease in the applied voltage can be explained
if we consider the presence of internal resistance Rseries , including
that designated as Rsox , which we associate with the progressive
redox reactions at the Au electrode. The internal series voltage
(I × Rseries ) can be extracted from the measurements using the
relationship:
Vcell = Vapplied − Vseries = Vapplied − I × Rseries (8)

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where Vapplied is the applied voltage, Vseries is the voltage due to
Rseries , and I is the set current. The calculated values of Vseries are
illustrated in Figure 8e. It is noteworthy that Vseries tends to ap-
proach zero beyond 100 Hz, as higher frequencies render redox
reactions unable to sustain Au oxidation because they are slower,
avoiding the development of Rsox and eliminating any parasitic
internal voltage drop (Figure 8c,d).
In the case of the effect that frequency has on the maximum
current and resistance of the LRS and HRS states, the motion
of oxygen vacancies, which is highly frequency dependent, may
be the cause. In particular cases, the modulation of the maxi-
mum current in memristors is an essential aspect of multilevel
switching.[40,41] Typically, the test equipment adjusts the com-
pliance current Icc (maximum) by incorporating diverse resis-
tors into the circuit’s configuration. However, different investi-
gations have demonstrated that self-limiting behavior can be in-
troduced by integrating at least two materials with distinct resis-
tances within the oxide electrolyte. Hardtdegen et al.[42] observed
multilevel switching utilizing a Ti/TiO2 /HfO2 trilayer as the elec-
trolyte, Kyung et al.[43] employed a Ta2 O5 /TaOx bilayer, while Fan-
tini et al.[44] showcased the potential of metal/electrolyte junc-
tions such as TiN/Hf/HfO2 to induce this effect. Turning to
our Ru/YSZ(100 nm) /Au cell, the series resistances and multilevel
switching stem from the variations in conductivity within the
internal p-i-n regions, as stated in Section 2.1.2. A comparative
analysis of maximum SET/RESET currents against the calculated
Rseries from Equation 8 is depicted in Figure 8f. The influence of
series resistance is most pronounced during the RESET process.
As the frequency ranges from 5 to 50 Hz, we notice a decrease
in the hysteresis area, moving toward an almost reversible be-
havior. With increasing frequency, a predictable reduction in the
hysteresis width is anticipated.[45] This change can be attributed
to the fact that the transported Ovac struggle to keep up with the
rapid changes in the applied signal’s speed (frequency). Figure 8g
shows the resistance of the HRS state and LRS state as a func-
tion of frequency, where it is observed that starting from 100 Hz,
the hysteresis width between the resistance of the HRS and LRS
states disappears.
Interestingly, within 200 Hz to 100 kHz (Figure 8c,d), the hys-
teresis area experiences an increase, resembling characteristics
often associated with ferroelectric materials.[46] In ferroelectrics,
this phenomenon primarily stems from internal polarization.
For our Ru/YSZ(100 nm) /Au cell, the internal local polarization
emerges from the internal p-i-n regions, which remain constant
during the stable LRS state. Furthermore, the change in the hys-
teresis loop’s direction correlates with a more significant contri-
bution from electron trapping at the interfaces between YSZ and
the metal.
In summary the Ru/YSZ(100 nm) /Au cell shows three distinct
operational regimes, each of which exhibits memristive proper-
ties that are frequency-dependent: Memristive behavior in the
frequency range of 5–50 Hz, the internal p-i-n junction behav-
ior from 100–500 Hz, and capacitive behavior by significant elec-
tron trapping within 1–100 kHz. These operational regimes are
visually represented in Figure 8h–k, alongside a proposed cir-
cuit model designed to identify the parasitic resistances in the
Ru/YSZ(100 nm) /Au cell. It is evident that at higher frequencies,
the conductive filament, i-region, and Au oxidation cease to be
prominent, resulting in a capacitive behavior. Simultaneously,
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electron trapping becomes more pronounced due to the reduced
impedance of the cell.
2.2.3. Voltage Sweeps and Temperature Dependence
The effect of temperature on the current-voltage curves for the
Ru/YSZ(100 nm) /Au cell is illustrated in Figure 9a,b. The experi-
mental setup was a temperature range from 100 to 170 °C, with a
constant voltage of 4 V. The superimposed voltage sweep remains
at ± 5 V at a frequency of 30 Hz, as in the preceding section.
With ascending temperatures, both the current response and
the hysteresis increased. The emergence of the pinched hystere-
sis loop aligns closely with the temperature range of 110°C to
120°C, corresponding to the lower threshold temperature for the
onset of electromigration (Section 2.1.5).
The increase in the hysteresis window and the current re-
sponse with temperature can be attributed to higher ion diffusiv-
ity, as stated in Equation 1. On the other hand, it is also observed
that the increase in the operating temperature reduces the thresh-
old voltage for the LRS state, as shown in Figure 9c.
At 110 °C, the required voltage for activating the LRS state (Vset )
is ≈2.7 V; with the temperature increasing to 170 °C, this value
decreases to approximately 2 V. In contrast, the voltage for deac-
tivating the LRS state (Vreset ) remains at 1.55 V.
As temperature increases, the probability of oxygen vacancy
creation within the material, particularly YSZ in this context, in-
creases. This phenomenon aligns with the solid-state theory and
can be quantified using the equation[47] :
1
P = (9)
1 + eEv ∕kB T
Here, Ev is the energy required for vacancy creation, kB is Boltz-
mann’s constant, and T is the temperature. The decrease in Vset
results from the increased probability of creating oxygen vacan-
cies with increasing temperature, facilitating their migration.
The Vreset constancy can be attributed to maintaining the initial
HRS state through the constant application of 4 V.
Figure 9d shows the conductance of the HRS and LRS states
within an Arrhenius plot. The curves 120 to 170 °C were fitted,
excluding 100 and 110 °C due to the incomplete formation of the
pinched hysteresis loop. The activation energy for the HRS state
was calculated at 68.5 kJ mol−1 or 0.71 eV, while for the LRS state,
it amounts to 66.5 kJ mol−1 or 0.69 eV.
2.2.4. Cooling the Ru/YSZ(100 nm) /Au Cell while Sustaining the
Switching Mechanism
In this experiment, we explore the cooling process of the
Ru/YSZ(100 nm) /Au cell from 170 °C down to 100 °C while ensur-
ing the continuous operation of the switching mechanism. The
cell was subjected to the same conditions: a constant 4 V, a ±5 V
superimposed sweep, and a 30 Hz frequency. Unlike the previous
section, where the voltage signal was turned off during tempera-
ture transitions, the voltage signals remained active throughout
the cooling process. The schematic representation and resulting
current curves are depicted in Figure 9e,f.
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Figure 9. Temperature effect on the current response to the voltage sweeps in the applied to the Ru/YSZ(100 nm) /Au cell. a) Applied signal, b) Current-
voltage curves between 100 – 170 °C with constant 4 V and superimposed ±5 V sweeps at 30 Hz. c) Temperature dependence of SET and RESET voltages.
d) Arrhenius plot of the HRS and LRS states. Second experiment. e) Applied signal, f) Current response of the Ru/YSZ(100 nm) /Au cell from 170 to 100 °C
while maintaining an active voltage signal. Conditions include a constant 4 V, a superimposed ±5 V sweep at 30 Hz. g) Temperature-dependent Set and
Reset Voltages. h) Arrhenius plot illustrating the HRS and LRS states’ behavior across temperatures.

A notable observation arises as the sample is gradually cooled
to 100°C: the SET voltage remains constant at 2 V across all tem-
peratures (Figure 9g). This contrasts with the previous section,
where the SET voltage exhibited a range of values from 2.7 V at
100 °C to 2 V at 170 °C. Also, the pinched hysteresis loop persists
up to 100°C as the temperature is lowered without discontinuing
the applied voltage signal. Additionally, the RESET voltage main-
tains its value at 1.55 V throughout. Constructing an Arrhenius
plot based on the conductance data reveals a consistent curve that
spans the entire temperature range (Figure 9h). The extracted
activation energy for the HRS and LRS states is 60.2 kJ mole−1
or 0.65 eV. These slightly diminished values can be anticipated,
as the initial energy input from the potential is not required at
each temperature. The initial temperature of 170 °C might have
induced additional electronic/ionic charges, effectively “locking”
the SET/RESET voltages.
3. Conclusion
through the electrolyte as the rate-limiting step has essential im-
plications for memristor design. Researchers can explore modifi-
cations to electrolyte composition, crystal structures, scaled-down
physical thickness, or defect densities to improve ion mobility
and facilitate faster switching.
The used model highlights the nature of the incubation time
necessary for the onset of electromigration, which exhibits a lin-
ear correlation with the inverse of the applied voltage squared,
regardless of the species transported, as explained in Equation 1.
We emphasize the importance of identifying the switching reac-
tion in current measurements over time to examine critical pa-
rameters such as threshold voltage and LRS state stability rather
than relying solely on I-V curve sweeps. Lastly, the exploration
of thermal activation of electromigration not only provides in-
sights into charge carriers through activation energy calculations
but also sheds light on potential transitions to alternate transport
mechanisms, contributing to a more profound understanding of
the overall behavior.

In this study, we investigated the fundamental aspects of memris-

tive switching kinetics in metal/electrolyte/metal cells, where the
rate-limiting process depends on the diffusion of metal atoms,
oxygen vacancies, or oxygen ions through the electrolyte.
The exemplification of the model on the memristive switch-
ing behavior of the Ru/YSZ(100 nm) /Au cell elucidates different
voltage- and frequency-dependent phenomena, encompassing
electronic conduction, charge trapping, redox processes, valence
changes, oxygen vacancy migration, ion conduction, and conduc-
tive filament formation/annihilation.
The parameters mentioned above, such as the diffusion con-
stant of the electrolyte and the threshold voltage that governs
the behavior, were calculated by applying the model to different
cells highlighted in the literature. Identifying the ion migration
4. Experimental Section
Fabrication of the Device Structure: The thin-film device was fabricated
on p-type (100) silicon wafers and followed a Metal/Insulator/Metal struc-
ture, with Ru as the lower electrode, YSZ as the electrolyte, and Au as the
upper electrode.
To fabricate the Ru and YSZ, Atomic Layer Deposition (ALD) was em-
ployed in a Beneq TFS-200 system. First, a 40 nm Al2 O3 layer was de-
posited to enhance adhesion to the Ru layer and electrically isolate it from
Si. The Al2 O3 deposition occurred at 250 °C, utilizing trimethylaluminum
(TMA, Strem chemicals) as the precursor and water (H2 O) as the oxidiz-
ing agent.
Next, as the lower electrode, a 30 nm thick Ru metal film
was deposited at 350 °C, utilizing bis(ethyl-cyclopentadienyl), ruthe-
nium (Ru(EtCp)2 , Strem chemicals), and oxygen (O2 ) as precursors.

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Following this, 100 nm of YSZ was grown at 250 °C by alternately de-
positing 4 cycles of ZrO2 (growth rate of 0.8 Å per cycle) and 1 of
Y2 O3 (growth rate of 1.1 Å per cycle). The precursors for YSZ were
tetrakis(ethylmethylamino)zirconium (TEMAZr, Strem chemicals), and
tris(methylcyclopentadienyl)yttrium (Y(MeCp)3 , Strem chemicals) com-
bined with H2 O. Finally, the upper Au electrode was thermally evaporated
in circular patterns of 760 μm diameter using a shadow mask on a JEOL
JEE-400 PVD system, resulting in a 30 nm thick Au layer.
The comprehensive material characterization of the fabricated cells had
been thoroughly presented in the previous works.[26,48,49] The analysis in-
cludes the structural, surface, vibrational, and optical properties.
Electrical Characterization: Electrical measurements were conducted
in an air atmosphere from 100 to 170 °C. For the electrical circuit connec-
tion, gold-plated needle probes affixed to micromanipulators (Semiprobe)
were employed for both the lower and upper electrodes. To apply voltage
signals, a source meter unit (SMU, Keithley 2450) and a wave function gen-
erator (Rigol G1022Z) were utilized. The response current was then mea-
sured using the same SMU and an oscilloscope (Tektronix DPO2004B). All
electrical measurements were performed inside a Faraday cage to mitigate
the influence of external electrical interference (noise).
Acknowledgements
J.V. and H.T. acknowledge the financial support by DGAPA-UNAM Grants
No. IN108821, IN119023. FORDECYT Grants No. 272894 and 21077;
CONAHCyT Grant No. A1-S-21323, and FONCICyT Grant No. 246648. To
CONACyT for the scholarship for postgraduate studies No. 613752. The
authors J.V. and H.T. acknowledge the technical support of J.A. Díaz, E.
Aparicio, E. Murillo, L. Arce, and D. Domínguez.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the cor-
responding author upon reasonable request.
Keywords
atomic layer deposition, incubation time, ion diffusion coefficient,
memristor switching kinetics, switching time, threshold voltage, Yttria-
stabilized zirconia
Received: September 8, 2023
Revised: September 27, 2023
Published online:
[1] S. H. Jo, T. Chang, I. Ebong, B. B. Bhadviya, P. Mazumder, W. Lu, Nano
Lett. 2010, 10, 1297.
[2] L. Chua, Appl. Phys. A 2011, 102, 765.
[3] W. Sun, B. Gao, M. Chi, Q. Xia, J. J. Yang, H. Qian, H. Wu, Nat. Com-
mun. 2019, 10, 3453.
[4] D. Ielmini, S. Menzel, in Resistive Switching: From Fundamentals of
Nanoionic Redox Processes to Memristive Device Applications (Eds: D.
Ielmini, R. Waser), John Wiley & Sons, Hoboken, NJ 2016, p. 317–340.
[5] L. Goux, S. Spiga, in Resistive Switching: From Fundamentals of
Nanoionic Redox Processes to Memristive Device Applications (Eds: D.
Ielmini, R. Waser), John Wiley & Sons, Hoboken, NJ 2016, pp. 363–
394.
Adv. Electron. Mater. 2023, 2300608 2300608 (13 of 14)
2199160x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aelm.202300608, Wiley Online Library on [17/11/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advelectronicmat.de
[6] S. Menzel, J.-H. Hur, in Resistive Switching: From Fundamentals of
Nanoionic Redox Processes to Memristive Device Applications (Eds: D.
Ielmini, R. Waser), John Wiley & Sons, Hoboken, NJ 2016, pp. 395–
436.
[7] R. Waser, D. Ielmini, H. Akinaga, H. Shima, H.-S. P. Wong, J. J. Yang,
S. Yu, in Resistive Switching: From Fundamentals of Nanoionic Redox
Processes to Memristive Device Applications (Eds: D. Ielmini, R. Waser),
John Wiley & Sons, Hoboken, NJ 2016, pp. 1–30.
[8] S. Dirkmann, T. Mussenbrock, AIP Adv. 2017, 7, 065006.
[9] A. Wedig, M. Luebben, D.-Y. Cho, M. Moors, K. Skaja, V. Rana, T.
Hasegawa, K. K. Adepalli, B. Yildiz, R. Waser, I. Valov, Nat. Nanotech-
nol. 2015, 11, 67.
[10] R. Waser, 2008 Int. Electron Devices Meet. IEDM, San Francisco, CA,
USA, December 2008.
[11] M. Cassinerio, N. Ciocchini, D. Ielmini, Adv. Mater. 2013, 25, 5975.
[12] Y. Yang, P. Gao, S. Gaba, T. Chang, X. Pan, W. Lu, Nat. Commun. 2012,
3, 732.
[13] G.-S. Park, Y. B. Kim, S. Y. Park, X. S. Li, S. Heo, M.-J. Lee, M. Chang,
J. H. Kwon, M. Kim, U.-I. Chung, R. Dittmann, R. Waser, K. Kim, Nat.
Commun. 2013, 4, 2382.
[14] S. Menzel, U. Böttger, M. Wimmer, M. Salinga, Adv. Funct. Mater.
2015, 25, 6306.
[15] S. A. Chekol, S. Menzel, R. W. Ahmad, R. Waser, S. Hoffmann-Eifert,
Adv. Funct. Mater. 2022, 32, 2111242.
[16] S. Siegel, C. Baeumer, A. Gutsche, M. Von Witzleben, R. Waser, S.
Menzel, R. Dittmann, Adv. Electron. Mater. 2021, 7, 2000815.
[17] T. Tsuruoka, K. Terabe, T. Hasegawa, M. Aono, Nanotechnology 2010,
21, 425205.
[18] R. Kirchheim, Solid State Ionics 2018, 320, 239.
[19] R. Kirchheim, Acta Mater. 2019, 175, 361.
[20] R. Kirchheim, Acta Metall. Mater. 1992, 40, 309.
[21] J. L. Vazquez-Arce, H. Tiznado, R. Kirchheim, Acta Mater. 2022, 229,
117826.
[22] C. Cheng, Y. Li, T. Zhang, Y. Fang, J. Zhu, K. Liu, L. Xu, Y. Cai, X. Yan,
Y. Yang, R. Huang, J. Appl. Phys. 2018, 124, 152103.
[23] D. V. Guseinov, D. I. Tetelbaum, A. N. Mikhaylov, A. I. Belov, M. E.
Shenina, D. S. Korolev, I. N. Antonov, A. P. Kasatkin, O. N. Gorshkov,
E. V. Okulich, V. I. Okulich, A. I. Bobrov, N. V. Malekhonova, D. A.
Pavlov, E. G. Gryaznov, Int. J. Nanotechnol. 2017, 14, 604.
[24] S. Tikhov, O. Gorshkov, I. Antonov, A. Morozov, M. Koryazhkina, D.
Filatov, Adv. Condens. Matter Phys. 2018, 2018, 2028491.
[25] M. Yu, S. Grasso, R. Mckinnon, T. Saunders, M. J. Reece, Adv. Appl.
Ceram. 2016, 116, 24.
[26] O. A. Romo Jiménez, R. L. Noda, J. Portelles, J. L. Vázquez Arce,
E. Iñiguez, C. A. López Mercado, F. Solorio, J. Rebellon, J. Read, H.
Tiznado, Energy 2022, 253, 124199.
[27] W. Weppner, Electrochim. Acta 1977, 22, 721.
[28] F. Messerschmitt, M. Kubicek, S. Schweiger, J. L. M. Rupp, Adv. Funct.
Mater. 2014, 24, 7448.
[29] G.-H. Buh, I. Hwang, B. H. Park, Appl. Phys. Lett. 2009, 95, 142101.
[30] J. Claus, M. Leonhardt, J. Maier, J. Phys. Chem. Solids 2000, 61, 1199.
[31] N. Banno, T. Sakamoto, N. Iguchi, H. Sunamura, K. Terabe, T.
Hasegawa, M. Aono, IEEE Trans. Electron Devices 2008, 55, 3283.
[32] J.-M. Wen, S.-L. Chang, J. W. Burnett, J. W. Evans, P. A. Thiel, Phys.
Rev. Lett. 1994, 73, 2591.
[33] M. Lübben, S. Menzel, S. G. Park, M. Yang, R. Waser, I. Valov, Nan-
otechnology 2017, 28, 135205.
[34] W. Wang, E. Covi, Y.-H. Lin, E. Ambrosi, A. Milozzi, C. Sbandati, M.
Farronato, D. Ielmini, IEEE Trans. Electron Devices 2021, 68, 4342.
[35] H. Jiang, D. Belkin, S. E. Savel’ev, S. Lin, Z. Wang, Y. Li, S. Joshi, R.
Midya, C. Li, M. Rao, M. Barnell, Q. Wu, J. J. Yang, Q. Xia, Nat. Com-
mun. 2017, 8, 882.
[36] X. Ji, S. Hao, K. Y. Pang, K. G. Lim, R. Zhao, IEEE Electron Device Lett.
2020, 41, 505.
© 2023 The Authors. Advanced Electronic Materials published by Wiley-VCH GmbH

www.advancedsciencenews.com
[37] R. Schmitt, M. Kubicek, E. Sediva, M. Trassin, M. C. Weber, A. Rossi,
H. Hutter, J. Kreisel, M. Fiebig, J. L. M. Rupp, Adv. Funct. Mater. 2019,
29, 1804782.
[38] J. D. McBrayer, R. M. Swanson, T. W. Sigmon, J. Electrochem. Soc.
1986, 133, 1242.
[39] M. Kilo, C. Argirusis, G. Borchardt, R. A. Jackson, Phys. Chem. Chem.
Phys. 2003, 5, 2219.
[40] H. Manem, J. Rajendran, G. S. Rose, ACM J. Emerg. Technol. Comput.
Syst. 2012, 8, 6.
[41] M. Park, S. Park, K. H. Yoo, ACS Appl. Mater. Interfaces. 2016, 8, 14046.
[42] A. Hardtdegen, C. La Torre, H. Zhang, C. Funck, S. Menzel, R. Waser,
S. Hoffmann-Eifert, 2016 IEEE 8th Int. Mem. Work. IMW, Paris,
France, May 2016.
[43] K. M. Kim, S. R. Lee, S. Kim, M. Chang, C. S. Hwang, Adv. Funct. Mater.
2015, 25, 1527.
Adv. Electron. Mater. 2023, 2300608 2300608 (14 of 14)
2199160x, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aelm.202300608, Wiley Online Library on [17/11/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advelectronicmat.de
[44] A. Fantini, D. J. Wouters, R. Degraeve, L. Goux, L. Pantisano, G. Kar, Y.
Y. Chen, B. Govoreanu, J. A. Kittl, L. Altimime, M. Jurczak, presented
at 2012 4th IEEE Int. Mem. Work. IMW 2012, Milan, Italy, May 2012.
[45] M. Maestro-Izquierdo, M. B. Gonzalez, F. Campabadal, J. Sune, E.
Miranda, IEEE Electron Device Lett. 2021, 42, 565.
[46] Z. G. Lu, G. Calvarin, Phys. Rev. B 1995, 51, 2694.
[47] C. Kittel, P. McEuen, Introduction to solid state physics, https:
//www.wiley.com/en-ie/Kittel%27s+Introduction+to+Solid+State+
Physics%2C+8th+Edition%2C+Global+Edition-p-9781119454168
(accessed: October 2022).
[48] J. L. Vazquez-Arce, L. T. Lam, C. López-Mercado, G. Soto, H. Tiznado,
J. Am. Ceram. Soc. 2023, 106, 7567.
[49] J. L. Vazquez-Arce, O. Romo, F. Solorio, C. A. López-Mercado, J. Read,
D. Dominguez, O. E. Contreras, G. Soto, H. Tiznado, J. Power Sources
2022, 537, 231555.
© 2023 The Authors. Advanced Electronic Materials published by Wiley-VCH GmbH