Applied Surface Science 637 (2023) 157785

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Applied Surface Science

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Full Length Article

Enhanced resistive switching of silver copper iodide thin films prepared by

interfacial phase formation
Ji-Hyun Cha a, *, Jong Yun Kim b, Young-Jun Yu b, c, Duk-Young Jung d, *
a
Department of Chemistry, Chungnam National University, 99 Daehak-ro, Daejeon 34134, South Korea
b
Institute of Quantum Systems (IQS), Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon 34134, South Korea
c
Department of Physics, Chungnam National University, 99 Daehak-ro, Daejeon 34134, South Korea
d
Department of Chemistry, Sungkyun Advanced Institute of Nanotechnology, Sungkyunkwan University, Suwon, Gyeonggi-do 16419, South Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Resistive random-access memory (ReRAM), an alternative to conventional charge storage memory, employs the
Silver copper iodide switching of a resistive material between high-resistance and low-resistance states, which can be generated by
Resistive memory the formation/dissolution of metal filaments bridging the two electrodes in the cell. Silver iodide (AgI) is a
Vapor-phase iodization
promising solid electrolyte for ReRAM cells, but its application is hindered by poor photostability and low
Interfacial phase formation
Low power memory
electrical conductivity. Herein, a Cu-substituted β-AgI system, β′-Ag0.7Cu0.3I, was successfully prepared via
sequential deposition of a Cu metal layer onto a AgI thin film by a galvanic reaction, which induced the spon­
taneous incorporation of Cu+ cations into the AgI lattice. Cu substitution at the Cu–AgI heterojunction interface
is a novel way to modulate the chemical composition and improve the resistive switching properties of intrinsic
polycrystalline AgI thin films. We compared the resistive switching properties of a ReRAM thin film devices
based on β′-Ag0.7Cu0.3I with those based on pristine β-AgI. This device exhibited enhanced performance with high
ON/OFF ratio (~104) and low working voltage compared with the β-AgI-based device. These results strongly
suggest that binary metal halide materials can serve as simple model systems for the efficient formation of metal
filaments and have potential low-cost, low-power memory applications.

1. Introduction making them candidate for next-generation nonvolatile ReRAM appli­

cations.[5] When a specific electric field is applied to the two electrodes
Resistive switching (RS) is an electrical effect in which the electrical facing each other, metal filaments are formed in the solid electrolyte
resistance level of a material periodically changes between a high- layer by an ECM reaction (i.e., writing process).[5–7] This system allows
resistance state (HRS, OFF state) and low-resistance state (LRS, ON electrical current to easily cross the insulating section through con­
state) according to the specific direction of the bias voltage.[1,2] ducting filaments (CFs). The metal filaments are then dissolved by
Because the different logic states can be represented by Boolean values applying bias voltage in the opposite direction (i.e., erasing process).
of 1 and 0, the application of this phenomenon in resistive random- Thus, in ECM cells, the non-volatile ON and OFF logic states are
access memories (ReRAMs) has attracted significant attention.[3] generated by the formation and removal of metal filaments, which can
Although various physical phenomena lead to nonvolatile resistive be controlled by the direction of the applied voltage between the two
change, RS can be induced by electrochemical metallization (ECM), electrode systems.[8].
valency change mechanism (VCM), or thermochemical mechanism The materials for ECM cells are Ag and Cu metal for the active
(TCM), which is based on redox-related chemical reactions.[4] ECM electrodes and Pt, indium tin oxide (ITO), and W for the inert electrodes.
cells are typically composed of a solid material acting as an insulator (I) Soluble elements in the solid electrolyte and electrochemically non-
or electrolyte (E) sandwiched between active and inert metal electrodes dissolvable counterparts are also included.[9] For the RS layer, silicon
(M) in a capacitor-like MIM or MEM structure.[3] They have a simple oxide (SiO2), germanium chalcogenide (GeSx and GeSex), and transition
device structure, low operating voltage and current (compared with metal oxide (ZrO2, WO3, and TiO2) are generally used.[7,10] However,
VCM and TCM cells), and easily modulated electrochemical behavior, these RS materials lose their cation transport properties and cause

* Corresponding authors.
E-mail addresses: [email protected] (J.-H. Cha), [email protected] (D.-Y. Jung).

https://doi.org/10.1016/j.apsusc.2023.157785
Received 4 April 2023; Received in revised form 31 May 2023; Accepted 13 June 2023
Available online 23 June 2023
0169-4332/© 2023 Elsevier B.V. All rights reserved.
J.-H. Cha et al. Applied Surface Science 637 (2023) 157785

damage to mechanical and electrical contacts during the redox cycle AgI thin film was synthesized according to a sequential iodization
reaction of the cations (Ag+ and Cu+) in the electrolyte.[11] Hybrid method reported in the literature.[20] ITO bottom electrodes with a
organic–inorganic halide perovskite, an attractive material owing to its dimension of 2 cm × 2 cm were cleaned with acetone and isopropyl
low ion migration energy, has been used as an insulating layer, but it has alcohol (IPA) under ultrasound irradiation. A high-purity Ag metal
low stability under humid and air conditions.[12,13] To minimize precursor layer with a thickness of 90 nm was deposited onto the
chemical damage to the cation transporting layer, AgI and Ag2S, known cleaned ITO substrate using a thermal evaporation system (REP-5004,
as an n-type semiconductor and ionic conductor, has attracted signifi­ SNTEK). The Ag-metal-coated ITO substrates were stored with 0.1 g of
cant attention as a RS material for the insulating layer of ReRAM de­ iodine under ambient conditions for 10 min. The Cu and Ag metal layers
vices. [14–19] Typically, dense and uniform polycrystalline AgI thin were thermally evaporated on the as-synthesized AgI substrates with
films are prepared by physical deposition and the iodization reaction thicknesses of 20 and 200 nm, respectively. To study the crystal struc­
between the metal precursor and iodine vapor.[16,20] Ag+ cations are ture, XRD (Ultima IV, Rigaku) was performed. The surface morphologies
mobile species that can be reduced to Ag metal filaments in the soft of the AgI thin films were studied via atomic force microscopy (NX10,
lattice of AgI by the application of an external electric field. However, Park systems). The electrical characteristics of the ReRAM cells were
the low photochemical stability and electrical conductivity of AgI thin measured using a semiconductor analyzer (4145B, Hewlett-Packard)
films pose challenges to their electronic device applications. under ambient atmosphere.
In previous study, these limitations addressed by introducing a
protection layer and employing chemical modulation methods.[20] 3. Results and discussion
Copper iodide (CuI) was employed as a protection layer against the
photodecomposition of the β-AgI layer under ambient atmosphere. The fabrication of the AgI-based ReRAM device is illustrated in
Additionally, the Fermi level and bandgap energy of a AgxCu1− xI alloy Fig. 1a. The appropriate thickness and crystalline phase of the metal
system, which can be either n- or p-type depending on the Ag/Cu ratio, layer were adjusted for ReRAM applications. A Ag metal layer with a
were tuned.[20,21] These investigations open the possibility of thickness of 90 nm was deposited onto an ITO substrate by a thermal
designing the heterojunction of a metal-halide-based semiconductor evaporation method. A AgI thin film with a thickness of 300 nm was
device by interfacial chemical substitution of Cu and Ag cations, which synthesized by the reaction of the Ag metal precursor and iodine vapor
can be carefully monitored by crystallographic and electrical analyses. under a mild atmosphere. After iodization, a smooth, transparent AgI/
This Ag–Cu–I multilayer system can be applied to not only hetero­ ITO thin film was obtained. When the Ag metal layer with a face-
junction p-n diodes, but also ReRAM devices. However, chemical, and centered cubic unit cell (fcc) was transformed to β-AgI with a hexago­
electrical studies on AgI and its derivatives for optoelectronic applica­ nal unit cell (wurtzite), the thickness of the layer increased 3.9 times
tions are currently insufficient. Particularly, a better understanding of because of the unit cell expansion.[20] Using an optimized thickness of
the effects of cation substitution on thermodynamics and ion dynamics is 90 nm for the Ag metal precursor layer produced well-developed crys­
required. This knowledge will aid not only the development of ReRAM talline grains of the AgI layer. As shown in Fig. 1b,c, the grain size of the
applications, but also in understanding the degradation of electrical AgI thin film synthesized using a thick Ag precursor layer (90 nm) was
performance due to metal cation migration and the structural defect of larger than that synthesized using a thin Ag layer (30 nm). Because the
hybrid organic–inorganic halide perovskite materials.[22–24]. electrical conductivity of AgI is lower than its ionic conductivity, we
Herein, we investigated the effect of Cu cation substitution on the RS hypothesized that larger grains of polycrystalline AgI films can help
properties of AgI by employing pristine β-AgI and Cu-substituted β′-AgI, reduce the contact resistance between the grain boundaries, leading to
denoted as β′-Ag0.7Cu0.3I, as the RS materials in a sandwich type ECM the efficient formation of electrical fields.[3] Because grain sizes below
cell. The ternary Ag–Cu–I-based cell consisted of an electrolyte covered 50 nm may cause a decrease in the concentration of mobile ions and/or
at the top and bottom by Ag (active electrode) and ITO (inert electrode), defects due to the de-doping effect, the growth of AgI crystallites with a
respectively. The β′-Ag0.7Cu0.3I thin film was successfully synthesized by large grain size is beneficial to the stable formation of metal filaments
the direct deposition of Cu metal onto the β-AgI layer. Specifically, a and transport of metal cations in the solid electrolyte system of ReRAMs.
galvanic reaction at the interface of the Cu and AgI heterojunction [25].
induced the transformation of β-AgI to the β′-Ag0.7Cu0.3I phase, whose A Cu metal with a thickness of 20 nm was selectively deposited onto
chemical composition and crystal structure were determined by X-ray the as-synthesized polycrystalline AgI thin film by thermal evaporation
diffraction (XRD). We compared the electrical characteristics of the using a dot-patterned shadow mask with a diameter of 100 μm. The
β-AgI- and β′-Ag0.7Cu0.3I-based ReRAM devices depending on the deposited Cu thin layer imparts endurance against AgI photodecompo­
applied potential. When the currents of the devices at the high-voltage sition, and the galvanic reaction at the interface of the AgI and Cu thin
from –3 to 1 V of the sweep range were collected, both devices films induces a phase transition from β-AgI to β′-Ag0.7Cu0.3I (a squeezed
showed a similar current–voltage (I–V) curve exhibiting the character­ wurtzite unit cell is denoted as the β′-phase).[20] Typically, a Cu thin
istic of a negative differential resistance effect. Interestingly, at the ± film has poor adhesion to the substrate surface. However, cation
0.1 V of the sweep range, the β-AgI-based device showed ohmic migration between the Cu and AgI layers facilitates the stable attach­
behavior, while the β′-Ag0.7Cu0.3I-based device showed excellent RS ment of the Cu layer onto the AgI surface. The Ag top electrode was
behavior with high ON/OFF ratio because its electrical property was deposited directly onto the Cu-coated AgI layer. Vertical stacks of Ag top
improved by interfacial chemical modification with Cu+ cations. To electrode/Cu/β′-Ag0.7Cu0.3I switching layer/ITO substrate were fabri­
elucidate the differences in the working processes of these devices, a cated. To compare the effect of Cu doping on the RS properties, a AgI-
mechanism of metal filament formation in the CuI–AgI alloy system was based ReRAM device was fabricated excluding the Cu deposition step
proposed. using the same process as the device with the Ag (200 nm)/AgI (300
nm)/ITO structure.
2. Materials and methods XRD was conducted to verify the crystal phase and cation ratio of the
AgxCu1-xI layer at each experimental step (Fig. 2a). The XRD pattern of
Materials Silver (3 mm shot, 99.99%) and copper (2–6 mm shot, the Ag metal precursor film (black solid line) showed a sharp and strong
99.999%) were purchased from Origin. Iodine (99.99%) and ITO-coated peak at 2θ = 38.09◦ , corresponding to the (1 1 1) plane of the fcc Ag
glass substrates were purchased from Sigma-Aldrich. Washing solvents metal, indicating that the film was highly oriented along the [1 1 1] di­
were purchased from Samchun Chemical. All metal and halogen sources rection. The minor peaks at 30.22◦ , 35.18◦ , and 44.34◦ corresponded to
were used without further purification. the ITO substrate (JCPDS 88–0773). After vapor-phase iodization of the
Fabrication and Characterization of ReRAM Devices The Cu-substituted Ag precursor layer, the XRD pattern of the resulting AgI layer (red solid

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J.-H. Cha et al. Applied Surface Science 637 (2023) 157785

Fig. 1. (a) Schematic illustration of the fabrication of the Cu/AgI heterojunction on the ITO substrate. The inset shows a photograph of the sample with four circular
cells. The scale bar represents 200 μm. Atomic force microscopy (AFM) images of AgI synthesized using an Ag metal layer with a thickness of (b) 30 and (c) 90 nm.

Fig. 2. (a) X-ray diffraction patterns of the Ag/ITO (black), AgI/ITO (red), Cu (20 nm)/AgI/ITO (blue), and Cu (150 nm)/AgI/ITO (green) thin films. Schematic
illustrations of the reaction mechanisms and atomic movements for (b) iodization and (c) interfacial phase transformation.

line, Fig. 2a) exhibited a sharp peak at 23.68◦ and three broad minor sputtering of Ag and Cu metal by vapor iodization, are generally used.
peaks at 39.17◦ , 42.67◦ , and 46.31◦ corresponding to the (0 0 2), (1 1 0), [21,26] In this work, the galvanic reaction at the interface of the Cu and
(1 0 3), and (1 1 2) planes of β-AgI, respectively. In a previous study, AgI heterojunction provided a more efficient way of forming not only
among the three AgI polymorphs, the β-AgI crystal phase was obtained the local structure of the Ag metal + AgI interface, but also the CuI–AgI
by the reaction of iodine vapor with the Ag metal oriented in the [1 1 1] solid solution. The formation of Ag clusters at the interface plays a
direction (Fig. 2b).[20]. crucial role in the formation of stable Ag electrode contacts.[14]
After the deposition of the Cu layer onto AgI, the XRD pattern (blue Moreover, the incorporation of CuI into the AgI medium is beneficial to
solid line, Fig. 2a) showed characteristic diffraction peaks corresponding RS performance because of the small effective mass and large electrical
to the β′-Ag0.7Cu0.3I and Ag metal phases. The three peaks of the conductivity of CuI.[3] Peaks related to Cu metal were not observed
β′-Ag0.7Cu0.3I phase were shifted to higher diffraction angles than those because the metal was too thin to be detected in the XRD pattern of the
of the pristine β-AgI phase. In our previous study, the chemical Cu (20 nm)/AgI/ITO sample. When a thicker Cu metal layer (150 nm)
composition of Ag(1-x)CuxI layer was confirmed through XRD patterns was deposited onto AgI, the peak of Cu appeared at approximately 44◦
according to Vegrad’s rule.[20] The chemical stoichiometry of (green solid line, Fig. 2a), and the chemical formula of the metal halide
β′-Ag0.7Cu0.3I was predicted based on the XRD pattern of the thin film. layer was confirmed as Ag0.7Cu0.3I, which is a saturated concentration of
The Ag metal peak appeared after the deposition of the Cu layer because Cu cations dissolved in the AgI lattice under our deposition condition.
oxidized Cu+ cations diffused into the AgI soft lattice, and Ag+ from AgI To compare the RS properties of the β-AgI- and β′-Ag0.7Cu0.3I-based
was subsequently reduced to Ag metal clusters by galvanic reaction ECM cells, the I–V curves were measured at room temperature by per­
(Fig. 2c).[20] In a previous study, Ag metal clusters were formed in the forming a DC sweep. Fig. 3 shows the characteristic I–V curves of the Ag/
AgI layer during the direct deposition of a thick Ag metal layer (200 nm) β-AgI/ITO (a, c) and Ag/Cu/β′-Ag0.7Cu0.3I/ITO (b, d) devices under
onto the AgI layer, which was confirmed by X-ray absorption spectros­ different potentials of the electric field applied to the Ag active electrode
copy.[14] To obtain CuI and AgI solid solutions, physical mixing and ITO inert electrode. To determine the RS characteristics in the high-
methods, such as ball-milling of AgI and CuI powder and magnetron co- voltage, the I–V curves of the ECM cells were recorded for three cycles by

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J.-H. Cha et al. Applied Surface Science 637 (2023) 157785

Fig. 3. Current–voltage (I–V) curves of (a, c) Ag/b-AgI/ITO and (b, d) Ag/Cu/b′-Ag0.7Cu0.3I/ITO devices in logarithmic scale. The switching characteristics of each
device were measured by applying high (±3 V) and low (under ± 0.5 V or ± 0.1 V) voltages. The inset diagrams show cross-sectional views of the device structures.

programmed sweeping of the voltage in the following sequence: − 3 V → other hand, upon employing a low-voltage (–0.1 to 0.1 V) with a small
0 V → +1.2 V → 0 V → − 3 V. In this potential range, both devices sweep interval (0.002 V), which led to only Cu ionization in the
exhibited bipolar RS behavior, in which the ON and OFF logic states β′-Ag0.7Cu0.3I-based cell, the contribution of the Cu metal filament to
were displayed depending on the polarity of the applied voltage. In low-voltage operation could be observed. Consequently, while the I − V
Fig. 3a, the first cycle curve of the AgI-based cell began in the HRS (OFF curve of the β-AgI-based cell exhibited ohmic behavior, indicating the
state) as the applied bias was increased from − 3 V to + 1.2 V, with the lack of resistivity change according to the applied voltage direction in
switch to the LRS (ON state) occurring at approximately + 0.2 V. The the ± 0.5 V (Fig. 3c), the β′-Ag0.7Cu0.3I-based cell showed clear RS
cell remained in the LRS until the reverse sweep reached − 1 V, at which characteristics in the ± 0.1 V (Fig. 3d). They had small ON and OFF set
point the current level of the cell gradually decreased and returned to voltages of 0.002 and 0 V, respectively. Although the resistances of the
the HRS. In 2nd and 3rd cycles, the AgI-based cell exhibited a similar LRS and HRS were in the order of kiloohms, they showed a higher ON/
curve shape, but the ON and OFF set voltages were different in each OFF ratio (~104) in the high-potential region than that in the low-
cycle because of the formation of Ag0 CFs in the highly resistive AgI solid potential region (~102). Therefore, the β-AgI-based cell showed
electrolyte.[2] As shown in Fig. 3b, the β′-Ag0.7Cu0.3I-based cell had typical ECM properties based on the AgI electrolyte, while the
similar RS characteristics to the pristine AgI-based cell, although it had β′-Ag0.7Cu0.3I-based cell exhibited two types of RS properties according
stable ON and OFF set potentials at 0.5 and − 0.54 V, respectively. to the power of the applied potential. The low operating voltage and
Because the incorporation of Cu into the AgI lattice increased the con­ high ON/OFF ratio of the β′-Ag0.7Cu0.3I-based cell in this work are
ductivity of AgI, β′-Ag0.7Cu0.3I provided more uniform electric fields and unique behaviors unlike those observed in previous studies on AgI-based
enabled a more stable formation of CFs than the pristine AgI medium ECM cells. Details of the RS properties of ReRAM cells based on the AgI
under the same applied potential.[20,21] This indicates that the incor­ and CuI electrolyte are summarized, and our results are compared with
poration of Cu into AgI enhances the writing/erasing cycle uniformity of those from previous studies in Table 1.
AgI-based ECM cells. Based on chemical and electrical observations, we propose that the
We also investigated the formation of Cu metal filaments originating working mechanism of AgI-based ReRAM devices depends on the
from Cu ionization under a low voltage (<0.1 V) without Ag ionization, incorporation of Cu. Without the Cu layer, the β-AgI-based ReRAM cell
which requires the application of a high voltage (>–3 V). Consequently, shows the general RS behavior of an ECM cell, as shown in Fig. 4a. When
the β-AgI- and β′-Ag0.7Cu0.3I-based cells showed notable RS performance Vset (0.6 V) is applied in the positive direction, the reduced Ag0 clusters
differences in the low-potential region, as shown in Fig. 3c,d. A detailed bridge the top and bottom electrodes, and then the electrical state
change in electrical characteristics ascribed to Cu ionization could not changes from the HRS to the LRS. Upon switching the voltage in the
be observed because of the simultaneous ionization of both Ag and Cu in negative direction at Vreset (–0.9 V), Ag metal filaments are dissolved in
the high-voltage (− 3 to1 V) with a large sweep interval (0.1 V). On the the AgI electrolyte, and the AgI cell returns to the HRS. Owing to the low

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J.-H. Cha et al. Applied Surface Science 637 (2023) 157785

Table 1
Summary of the resistive switching performance of resistive random-access memories based on AgI.
RS materials Thickness ON/OFF ratio ON state (LRS) OFF set state (HRS)

set potential (V) resistance (Ω) reset potential (V) resistance (Ω)

AgI film[16] 400 nm 104 0.01 ~26 0.33 ~105

AgI thin film[15] 30 nm – 0.08 < 1 × 103 <− 0.01 –
AgI thin film[14] 50 nm – 0.13 ~ 1 × 105 <− 0.01 –
AgI pellet[26] 1.25 mm 4.97 × 102 0 3 × 104 0.36, − 0.38 6.2 × 105
CuI[27] 20 nm > 101 − 1.5 V – 1.3 V –
AgI film* 300 nm 2.68 × 102 0.66 35.8 − 0.9 2.2 × 103
β′-Ag0.7Cu0.3I film* 300 nm 2.05 × 102 0.5 39.1 − 0.54 1.6 × 103
1.7 × 104 0.054 2.0 × 103 0 2.97 × 107
*
Our results.

Fig. 4. Sketched cross-sections of resistive switching behaviors in the AgI-based memristor (a) without and (b, c) with a Cu layer. Formation of conducting filaments
upon the application of (b) high and (c) low voltage to the β′-Ag0.7Cu0.3I-based cell.

electrical conductivity of AgI, the writing and erasing cycles of the Ag the AgI-based cell in the HRS and LRS probably because the Cu filament
metal filaments are unstable.[20,21] Redox reactions of the Ag ions do is thinner than the Ag filament. To determine the RS mechanism and
not occur below the Vset and Vreset potentials. As shown in Fig. 4b, the I redox reaction of the ReRAM cell based on the Ag − Cu − I system,
− V sweep of the β′-Ag0.7Cu0.3I-based cell shows a similar behavior to computational simulation and compositional analysis of the metal fila­
that of the pristine AgI-based cell but the former cell has better cycle ments are required.
uniformity owing to the enhancement of electrical conductivity upon Cu
incorporation in the AgI matrix.[20,21] Moreover, in the low-voltage 4. Conclusions
(±0.1 V), the I − V curve of the β′-Ag0.7Cu0.3I-based cell shows a clear
resistivity change with a high ON/OFF ratio, which is the best perfor­ In summary, the differences between the RS properties of β-AgI and
mance among the AgI-based ReRAM devices summarized in Table 1. We β′-Ag0.7Cu0.3I were investigated by comparing their chemical and elec­
believe this result may be related to the redox reaction of Cu cations in trical properties. A Cu-substituted AgI thin film was successfully pro­
β′-Ag0.7Cu0.3I. Cu+ can be reduced and moves more easily than Ag+ duced via galvanic reaction at the interface of the AgI layer, obtained by
because of its smaller cation size and effective mass (Fig. 4c). We hy­ vapor-phase iodization of Ag metal, and the deposited Cu thin film.
pothesize that the β′-Ag0.7Cu0.3I-based cell has a lower resistance than Crystallographic analysis confirmed that the crystal phase and saturated

5
J.-H. Cha et al. Applied Surface Science 637 (2023) 157785

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