JOURNAL OF NANO- AND ELECTRONIC PHYSICS ЖУРНАЛ НАНО- ТА ЕЛЕКТРОННОЇ ФІЗИКИ

Vol. 12 No 2, 02035(4pp) (2020) Том 12 № 2, 02035(4cc) (2020)

Resistive Switching Memory Properties of Electrodeposited Cu2O Thin Films

Rohini R. Patil1, Shubham V. Patil1, Amey M. Sabnis1, Kishorkumar V. Khot1,

Rajanish K. Kamat2, Tukaram D. Dongale1,*, Deok-kee Kim 3, †

Computational Electronics and Nanoscience Research Laboratory,

1

School of Nanoscience and Biotechnology, Shivaji University, Kolhapur, 416 004, India
2 Department of Electronics, Shivaji University, Kolhapur, 416 004, India
3 Department of Electrical Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul – 05006,
Republic of Korea

(Received 15 February 2020; revised manuscript received 15 April 2020; published online 25 April 2020)

The Cu2O thin film was developed using an electrodeposition approach for resistive memory applica-
tion. The impact of the deposition voltage (1V, 2V, 3V, and 4V) on resistive switching (RS)/memristive
properties of Cu2O thin films was studied. The XRD spectrum reveals that deposited Cu 2O has a cubic
crystal structure. The bipolar RS in Al/Cu2O/FTO device was clearly observed during the current-voltage
(I-V) measurement. The basic memristive properties were calculated from I-V data. The charge transport
studies suggested that the SCLC mechanism was responsible for device conduction, and RS was due to fil-
amentary effect. The result suggested that the electrodeposition technique is useful to fabricate a memris-
tive device for various applications.

Keywords: Electrodeposition, Cu2O, Resistive switching; Memristor.

DOI: 10.21272/jnep.12(2).02035 PACS numbers: 81.15.Pq, 77.80.Fm, 68.60. − p

1. INTRODUCTION ide (Cu2O) can be easily deposited on the conductive

The resistive switching (RS) is an exciting phenom-
enon, owing to the reversible change in the resistive
states of the device and therefore, can be used as a
memory device. Additionally, the RS devices have a
simple device configuration, making it a potential can-
didate for the crossbar memory application [1]. Moreo-
ver, the scalability and compatibility with the CMOS
process are also a few benefits of RS devices [2]. Re-
cently, memristive devices are extensively studied
based on RS effect for various applications that include
but not limited to the memory, sensor, logic and neu-
romorphic computing [3-4]. The RS devices are made
up of two electrodes and sandwiched active switching
layer. The external electric field forces a device for bi-
stable resistance switching and to store the data in the
form of the resistance.
In recent years, the RS devices are extensively de-
veloped and studied using solution-processable tech-
niques. This is because the solution-processable tech-
niques are inexpensive, simple, low-temperature pro-
cess and scalable [5]. On the other hand, the physical
deposition techniques such as atomic deposition tech-
niques or sputtering are expensive and sophisticated.
Given this, low cost and reliable memory devices are
the need of the hour to carry out the necessary research
and develop the end product. Among the many solution
deposition techniques, the electrodepositio0n technique
has multiple advantages. The electrodeposition method
provides good film quality with large area deposition
property which cannot be achieved by other techniques.
The electrodeposition technique is cost-effective and
takes a short time for uniform deposition of thin films
as compared with other methods [6].
In the case of the electrodeposition, the cuprous ox-
substrate. The Cu2O is good semiconducting oxide ma-
terials with a direct bandgap [7].
Here, we have used the electrodeposition technique
to deposited the Cu2O on FTO and investigated the
effect of the deposition voltage (1 V to 4 V) on the
RS/memristive properties of Cu2O thin films. In addi-
tion to this, we report the various memristive proper-
ties of the Al/Cu2O/FTO thin-film device. Moreover, the
conduction mechanism was investigated and proposed
the RS mechanism for the Al/Cu2O/FTO memristive
device.
2. EXPERIMENTAL
The electrodeposition of the Cu2O was carried out
by using the two-electrode single-compartment electro-
chemical cell.The schematic illustration of the Cu2O
deposition is shown in Fig. 1a. The FTO substrate was
used as a working electrode [8]. At the outset, the FTO
substrate was treated with ultra-sonication to remove
the dust and other surface impurities. Then it was
cleaned using acetone, dysol, and iso-propanol for 20
min and finally rinsed with double distilled water. Two
kinds of electrolyte solutions were used for the Cu2O
electrodeposition technique. The first electrolyte was
the aqueous solution of 1M CuSO4.5H2O and 6M sul-
phuric acid and the second electrolyte was the 4M sodi-
um hydroxide (NaOH) dissolved in de-ionized water.
Firstly, for the deposition of Cu, the Cu foil (anode) and
FTO (cathode) were dipped into the first electrolyte and
1-4 V was applied between two electrodes. For further
oxidation, Cu deposited FTO act as cathode whereas
graphite rod as an anode, both were dipped in NaOH
solution. Those of deposited film annealed in a furnace
at a temperature of 200°C for 90 minutes. The electro-

* tdd.snst@unishivaji.ac.in
† deokkeekim@sejong.ac.kr

2077-6772/2020/12(2)02035(4) 02035-1  2020 Sumy State University

ROHINI R. PATIL, SHUBHAM V. PATIL ET AL. J. NANO- ELECTRON. PHYS. 12, 02035 (2020)

deposition voltage was changed from 1 V to 4 V to
study the effect of deposition parameters on the RS
properties of Cu2O thin films. Aluminum (Al) top elec-
trode was fabricated using a vacuum deposition tech-
nique. The typical device structure used in the present
investigation is shown in Fig. 1b. The memristive prop-
erties of the Al/Cu2O/FTO thin-film device were detect-
ed with the help of the ArC ONE instrument.
(a) - +
+ -
RESET voltage. It is observed that the RESET voltages
tend to increases as the electrodeposition voltage in-
creases. This is due to the fact that the higher electro-
deposition voltage can form the thick film. Therefore,
higher RESET voltage is needed to switch the device
from one resistance state to another. However, the
same SET voltage was required for all devices for RS
operation, suggesting the SET voltage was independent
of electrodeposition voltage. In the present case, the
(c)
negative SET voltage switches the device from HRS to

(200)
4V

(311)
(220)
(111)
Copper Foil

LRS. The nature of the hysteresis loop is found to be

(200)
Cu2O
Cu
99999999999 FTO diverse for all Cu2O based devices. In particular, nega-
3V
tive differential resistance like I-V nature was noticed
for the 1 V and 3 V deposited Cu2O devices. This kind
Intensity (a.u.)

FTO CuSO4.5H2O+H2SO4 Growing of Cu Film NaOH Graphite

Rod
of negative differential resistance was also observed in
some other memristive devices [9-10].
Annealed at 200
oC for 2 hr

2V
Cu2O
-3 -3
4.0x10
(a) RESET 4.0x10
(b) RESET
+ - A -3 1 -3 1
(b) V V 2.0x10 2.0x10
3 3

Current (A)

Current (A)
0.0 0.0
2 2
1V -3 SET -3
-2.0x10 -2.0x10
-3 -3
-4.0x10 -4.0x10 4
4
-3
Al -6.0x10 -6.0x10
-3

Cu2O -8.0x10
-3
-8.0x10
-3 SET
30 40 50 60 70 80 90 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
FTO
2(Degree) Voltage (V) Voltage (V)
-3
-3
8.0x10
1.8x10 RESET
(c) RESET -3
(d)
Fig. 1  (a) schematic illustration of the Cu2O deposition
6.0x10
-3
1.2x10 -3
1 4.0x10
(b)device structure. (c)XRD spectra of Cu2O thin films deposit- -4
1
6.0x10

Current (A)
Current (A)

-3
3 2.0x10
ed at different voltages on the FTO substrate 0.0
SET 2 0.0
2
-4
3
-6.0x10 -2.0x10
-3

3. RESULT AND DISCUSSION

-3 4 -3
-1.2x10 -4.0x10
4
-3 -3
-1.8x10 -6.0x10
SET
The electrodeposited thin films were characterized
-3 -3
-2.4x10 -8.0x10
-1.0 -0.5 0.0 0.5 1.0 1.5 2.0 -1.0 -0.5 0.0 0.5 1.0 1.5

using XRD (D2 phaser), as shown in Fig. 1c. The elec- Voltage (V) Voltage (V)
trodeposition voltage-dependent XRD pattern suggest-
Fig. 2  I-V curves of the Cu2O based devices deposited at (a)
ed the presence of the significant peaks related to the
1V, (b) 2V, (c) 3V, (d) 4V. Arrows indicate the switching direc-
Cu2O. The XRD pattern shows that the intensity of the
tion
(200) crystal plane was higher as compared with the
other planes. The existence sharp peaks at 37.20°, The hysteresis loop observed in the Al/Cu2O/FTO based
42.72°, 64.97°, and 73.57° are correspond to (111), devices suggested that the electrodeposited developed
(200), (220), and (311)crystal planes, respectively. This devices possess memristive like properties. In order to
data matches appropriately to the cubic Cu2O structure better understand the memristive nature of all devices,
(JCPDS No. 65-3288). In addition to this, a peak at the flux and charge behavior was studied using exper-
50.75° is corresponding to the (200) plane of the metal- imental I-V data. The electrodeposition voltage-
lic Cu. It was observed that all deposited films show a dependent (1 V to 4 V) time-domain flux, time-domain
cubic Cu2O crystal structure. It was noticed that the charge and charge-flux characteristic of the
intense peak of the (200) crystal plane grows with the Al/Cu2O/FTO thin film memristive devices are depicted
deposition voltage. The crystallite size of deposited in Fig. 3. In the present case, the asymmetric flux
Cu2O at 1, 2, 3, and 4V was found to be 10.88 nm, 10.61 characteristic was observed for all Al/Cu2O/FTO based
nm, 11.36 nm, and 6.006 nm, respectively. memristive devices, as seen in Fig. 3a to d. This kind of
The developed Al/Cu2O/FTO thin film devices were asymmetric behavior is appeared due to the asymmet-
characterized using electrical measurements. The de- ric values of switching voltages. Similarly, the asym-
veloped four devices were tested for I-V measurements metric charge characteristic was observed for all
(Fig. 2). The hysteresis loop was obtained for all Al/Cu2O/FTO based memristive devices (Fig. 3e to h).
Al/Cu2O/FTO based devices, suggested the presence of The1 V and 2 V electrodeposited devices show negative
memristive like property in the devices. In the present charge values due to the active loop area under nega-
case, devices were tested in 0 V to ± 2V range, i.e., volt- tive bias are higher than positive bias. The charge-flux
age bias was swept as 0V → +2V → 0V→  2V → 0V. properties of all devices demonstrated a double valued
Initially, +5 V electroforming voltage was applied to the relation. This indicates that the Al/Cu2O/FTO devices
device for the proper operation. Initially, all devices are are non-ideal memristor devices or more Particularly
in the LRS, owing to the presence of a considerable they are memristive devices [11-12].The electronic
number of oxygen vacancies and ions due to the elec- conduction mechanism of developed devices can be
trodeposition process. These vacancies and ions could understood by the fitting different charge transport
be distributed randomly in the active switching layer. mechanism to the obtained I-V data (Fig. 4). In the
The device switch to HRS, as the voltage reaches to the

02035-2
RESISTIVE SWITCHING MEMORY PROPERTIES… J. NANO- ELECTRON. PHYS. 12, 02035 (2020)

0.18
LRS
Device Flux (Wb) 0.12
(a)
LRS
0.16 (b) LRS
0.15 (c) LRS 0.08 (d)

Device Flux (Wb)

Device Flux (Wb)

Device Flux (Wb)
0.10
0.12 0.12 HRS 0.06
0.08
0.09
0.06 HRS 0.08 0.04 HRS
HRS
0.06
0.04 0.02
0.04 0.03
0.02
HRS HRS
HRS HRS 0.00 0.00
0.00 0.00

0.00 0.05 0.10 0.15 0.20 0.25 0.00 0.06 0.12 0.18 0.24 0.30 0.00 0.05 0.10 0.15 0.20 0.25 0.00 0.05 0.10 0.15 0.20
Time (s) Time (s) Time (s) Time (s)
-4 -5
LRS 2.4x10 8.0x10
LRS
2.1x10
-4
(e) 1.8x10
-4 (f) (g) LRS 3.0x10
-4
(h) LRS

Device Charge (C)

Device Charge (C)
Device Charge (C)

Device Charge (C)

BCW -5
-4 BCW 6.0x10 -4
1.4x10 -4 2.4x10 BCW
1.2x10
-5 -4
7.0x10 -5 4.0x10
-5
1.8x10
HRS
6.0x10 BCW HRS
0.0 HRS HRS -4
A1 0.0 -5
1.2x10 A2
-5 A1 2.0x10 A2
-7.0x10 -5 HRS 6.0x10
-5

HRS
-6.0x10
-4 HRS HRS
-1.4x10 -4 0.0 A1 0.0 A1
A2 -1.2x10 A2

0.00 0.06 0.12 0.18 0.24 0.30 0.00 0.05 0.10 0.15 0.20 0.25 0.00 0.05 0.10 0.15 0.20 0.25 0.00 0.05 0.10 0.15 0.20

Time (s) Time (s) Time (s) Time (s)

-4
-4 2.4x10 6.00x10
-5
2.4x10
(i) LRS
N
BCW -4
(j) LRS
(k) LRS 3.0x10
-4
(l) LRS

Device Charge (C)

-4
1.8x10 N

Device Charge (C)

N
Device Charge (C)

1.8x10 BCW
Device Charge (C)

BCW -5
N
BCW -4
-4 -4 4.50x10 2.4x10
1.2x10 1.2x10
-5 -4
6.0x10 HRS -5 -5 1.8x10
6.0x10 3.00x10
0.0 HRS -4 HRS
A1 0.0 1.2x10 A2
-5 A1 -5
-6.0x10 1.50x10 HRS
-5 -5
-4 -6.0x10 A2 6.0x10
-1.2x10 HRS
HRS
-4 A2 HRS
-1.2x10
-4
A2 HRS 0.00 A1 0.0 A1
-1.8x10
0.00 0.03 0.06 0.09 0.12 0.15 0.18 0.00 0.03 0.06 0.09 0.12 0.00 0.03 0.06 0.09 0.12 0.00 0.02 0.04 0.06 0.08
Device Flux (Wb) Device Flux (Wb) Device Flux (Wb) Device Flux (Wb)

Fig. 3  Electrodeposition voltage-dependent (1 V to 4 V) (a-d) time-domain flux, (e-h) time-domain charge and (i-l) charge-flux
characteristic of the Al/Cu2O/FTO memristive devices

-4
2.4x10 4.5x10
-3

-4
1V
2V
Adj R =0.9998
2
(a) -2
10
1V
2V Adj. R =0.8977 (b) -3
1V
2V
2
Adj. R =0.9805
(c)
2.1x10 3V 3V 4.0x10 3V
2 4V
4V Adj R = Adj. R =0.9974 -3 4V
-4 Lineaar Fit 3.5x10
1.8x10 Linear Fit 0.9998 Linear Fit
-3 Adj. R2 =0.9970
Current (A)

Current (A)
Current (A)

-4
3.0x10
1.5x10 -3 Adj. R =0.9831 -3
10 2.5x10
-4 2
1.2x10 -3 Adj. R =0.9978
2
2.0x10
Adj R =0.9721
-5
9.0x10 Adj. R =0.9944 1.5x10
-3

-3
6.0x10
-5 -4 1.0x10
10 2
Adj. R =0.9688
-4
-5 5.0x10
3.0x10
2
Adj R =0.9997 0.0
0.0
0.05 0.10 0.15 0.20 0.25 0.30 0 1 2 3 4 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Voltage (V) Voltage (V )

2 Voltage (V)
-4
4.0x10
(f)
2 -3

-4
3.5x10
1V
2V
2
Adj. R =0.9331 (d) 1V
2V
Adj. R =0.9989
(e) 7.0x10 1V
2V
2
Adj.R =0.9989

Adj.R2 =0.9677
3V 2 -3
3V Adj. R =0.9977 6.0x10 3V
-4 4V
3.0x10 4V 4V
Lineaar Fit
Current (|A|)

Current (|A|)

Current (|A|)

Linear Fit -3 Lineaar Fit

2 5.0x10
-4
2.5x10 Adj. R =0.9902 2
-3 Adj.R =0.9629
10 -3
-4
4.0x10
2.0x10
-3
-4 3.0x10
1.5x10 2
Adj. R =0.9233
2
Adj. R =0.9836
2
-4 2.0x10
-3 Adj.R =0.9981
2
1.0x10 Adj. R =0.9896

-3
-5
5.0x10 1.0x10
2 -4
Adj. R =0.9895 10
0.0 0.0

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Voltage (|V|) Voltage (|V |)

2 Voltage (|V|)

Fig. 4  Electrodeposition voltage-dependent (1 V to 4 V) conduction mechanism fitting results of Al/Cu2O/FTO memristive devic-
es. Positive biased (a) low voltage region (HRS), (c) high voltage region (HRS)and (c) entire voltage region (LRS). Negative biased
(d) low voltage region (HRS), (e) high voltage region (HRS) and (f) entire voltage region (LRS)

present case, HRS of all devices follows the Ohmic and picted in Fig. 5. The electrodeposited Cu2O thin film
child’s square law at low and high voltage regions, has inherent oxygen vacancies and ions. These oxygen
respectively for both bias conditions. Alternatively, the vacancies and ions play a remarkable role in the RS
LRS I-V data were well fitted with the Ohmic conduc- process by developing the conductive filament in the
tion model. The Ohmic and Child’s square law fitting active switching layer. Initially, oxygen vacancies and
results of HRS suggested that SCLC was dominated in ions were randomly distributed in the active switching
the HRS [13]. The electrical result reveals that the layer, as shown in Fig. 5a. The electroforming process
developed memristive devices show the bipolar RS forces the oxygen vacancies and ions to forms the weak
characteristics with initial LRS. The initial LRS was conductive filament. This weak conductive filament is
observed due to a large number of defects present in responsible for the initial LRS instead of the HRS.
the thin film during the deposition process. Appling positive and negative voltage to the top and
The RS mechanism of the memristive devices is de- bottom electrode respectively, the oxygen vacancies

02035-3
ROHINI R. PATIL, SHUBHAM V. PATIL ET AL.
moved towards the bottom electrode, and oxygen ions
drift towards the top electrode, as shown in Fig. 5b. The
oxygen vacancies and ions based conductive filament
start to grow and current increases in the device with
respect to the increase in positive voltage on the top
electrode. At the RESET voltage, the Joule heating
process was dominated, results in the breaking of the
conductive filament, as shown in Fig. 5c.
(a) (b) (c)
+
+
Al Al Al
Cu2O Cu2O Joule heating
Cu2O
FTO _ FTO _ FTO
Initial State After RESET
Electroforming
Oxygen ion
Fig. 5  Possible RS mechanism of Al/Cu2O/FTO memristive
device. (a) Initial state, (b) device after electroforming process,
(c) RESET and (d) the SET process of the memristive device
Accordingly, the RESET voltage forces the device
into HRS due to the Joule heating. As the polarity of
the signal changes, the oxygen vacancies move towards
the top electrode and ions drift towards the bottom
electrode, as shown in Fig. 5d. This process leads to
form the highly-dense conductive filament and the
device again switches to the LRS. Given this, the alter-
nating polarity reversal can switch the device in two
resistance states and therefore, bipolar RS was ob-
served in the developed devices.
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An electrodeposition approach was used to develop
the Cu2O memristive devices and demonstrated the
bipolar RS characteristics. The XRD data of all thin
films are well matches with the cubic Cu2O structure
(JCPDS No. 65-3288). The average crystallite size of
deposited Cu2O at 1, 2, 3, and 4 V was found to be
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The analysis of electrical results suggested that the
Ohmic and SCLC are responsible for device conduction
and the filamentary mechanism was responsible for the
bipolar RS.
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02035-4