Applied Physics Express

LETTER
Recent citations
Manipulation of the electrical behaviors of - Architecture and Process Integration
Cu/MXene/SiO2/W memristor Overview of 3D NAND Flash Technologies
Geun Ho Lee et al

- Electrical Conduction Characteristic of a

2D MXene Device with Cu/Cr2C/TiN
To cite this article: Yuqi Wang et al 2019 Appl. Phys. Express 12 106504 Structure Based on Density Functional
Theory
Lei Wang et al

- LRS retention fail based on joule heating

View the article online for updates and enhancements. effect in InGaZnO resistive-switching
random access memory
Jun Tae Jang et al

This content was downloaded from IP address 182.75.45.1 on 26/08/2021 at 11:38

Applied Physics Express 12, 106504 (2019) LETTER
https://doi.org/10.7567/1882-0786/ab4233

Manipulation of the electrical behaviors of Cu/MXene/SiO2/W memristor

Yuqi Wang1 , Xinwei Liu1, Yihao Chen1, Wei Xu1, Dingkang Liang1, Fei Gao1, Miaocheng Zhang1, Subhranu Samanta3,
Xiao Gong3, Xiaojuan Lian1, Xiang Wan1, and Yi Tong1,2*
1
College of Electronic and Optical Engineering & College of Microelectronics, Nanjing University of Posts and Telecommunications, Nanjing 210023,
People’s Republic of China
2
Engineering Product Development, Singapore University of Technology and Design 487372, Singapore
3
Department of Electrical & Computer Engineering, National University of Singapore 117576, Singapore
*
E-mail: tongyi@njupt.edu.cn
Received May 22, 2019; revised July 30, 2019; accepted September 5, 2019; published online September 19, 2019

Electronic synapses with both long-term and short-term plasticity are considered as significant components for constructing brain-inspired
computing systems. Research progress on electrical synapses have proved that memristors possess huge similarities with biological synapses.
Nevertheless, an effective mean of manipulating the biological properties of memristors is still unclear. In this letter, we propose a memristor and
reveal that the compliance current of electroforming plays an active role in tuning short-term and long-term plasticity of the memristors. The results
may provide a useful guideline for manipulating memristor as electronic synapses in the hardware implementation of artificial neural networks.
© 2019 The Japan Society of Applied Physics

I
n recent years, the brain-inspired computing system has
attracted wide attention in both industry and academia. It
is generally believed that synaptic plasticity is critical for
human brains to achieve learning and computing ability.1,2)
As an important basis for brain-inspired systems, an elec-
tronic synapse with both long-term and short-term plasticity
shows great significance.3,4) The memristor, of which the
conductance can be modulated by the ionic transport in the
physical switching layer, stands out among many electronic
synapses candidates by virtue of their similarity to biological
synapse.5,6)
On the basis of that characteristic, the memristor-based
neural network algorithms and applications have been studied
and reported by scholars all over the world.7,8) Lu et al.
successfully implemented sparse coding algorithms, which is
believed to be a key mechanism in processing complex
sensory data, in a memristor crossbar array with very little
power consumption;9) Yang et al. replaced digital VMM
blocks with memristor-based DPE circuits in convolutional
neural network (CNN), showing a 14.8×, 5.5×, and 7.5×
improvement in throughput energy and computational den-
sity over the leading digital Application Specific Integrated
Circuit (ASIC).10)
Although some explorations have been performed, such as
introducing ferroelectric films into a memristor structure or
adopting special stimulus in experiments,11–13) the relevant
methods of designing and tuning of memristors are still
lacking. It is widely reported that different compliance
currents in electroforming have huge impacts on electrical
characteristics of memristors.14,15) However, recent researches
were limited to analyze the effects of electroforming on the
analog behavior or long-term plasticity of memristors.16,17)
Few works have been done to explore the effects on short-
term plasticity, which is crucial for achieving brain-inspired
computing systems.3,4,18)
In this work, we designed and fabricated a novel memristor
with insertion of MXene. The conductivity of 2D material
MXene differs according to the kind and proportion of
transition metals along with surface functionalities such as
−OH, −O, and −F.19–21) Therefore, MXene may present
high conductivity as well as semiconductor and insulator
properties. Moreover, it also possesses strong in-plane bonds
and weak coupling between layers together with the good
106504-1
possibility for emulating artificial biological synapses in
memristor.22–24) It is observed that the setting of compliance
current (Icomp) during electroforming significantly affect the
electrical responses of the memristor in terms of short-term
and long-term plasticity. The memristors electroformed with
different compliance currents have marked differences on the
paired-pulse facilitation (PPF) index and the influence of
pulse interval on PPF index. By controlling Icomp during
electroforming, memristors may present long-term potentia-
tion (LTP) and long-term depression (LTD) under a series of
positive and negative spike pulses. These results may provide
effective guidances on the design of memristor for the
application of achieving an electronic synapse with compre-
hensive learning and computing ability.
To fabricate the Cu/MXene/SiO2/W memristors, we use a
silicon wafer as substrate. Firstly, 90 nm Tungsten (W) was
deposited as the bottom electrode on the substrate via
physical vapor deposition (PVD). Then 80 nm SiO2 was
also deposited by PVD. Subsequently, the upper suspension
of the mixture of MXene (Ti3C2) power and water was spin-
coated onto the SiO2. Then, we drain excessive liquid by
evaporation to obtain the dense MXene films, as shown in
Fig. 1(a), and the thickness of MXene film is about 2.22 μm.
Finally, 100 nm Cu (500 μm × 500 μm) acting as top elec-
trodes were fabricated. The schematic illustration of the
fabricated Cu/MXene/SiO2/W memristors is shown in
Fig. 1(b).
All the electrical characteristics in this letter were tested by
Keithley 4200-SCS Semiconductor Characterization Analyzer
equipped with a four-probe system (Cascade S300). All
measurements were performed at room temperature in atmo-
spheric environment.
Electroforming process is considered as the method to
generate conductive channels in the memristor, and the
compliance current (Icomp) is a parameter set in electro-
forming process to prevent devices from breakdown.25,26) In
order to investigate the influence of Icomp in electroforming
processes on the following performances of the memristor,
Icomp of different values (10 μA, 500 μA) were set to initialize
pristine memristors. The electroforming profiles are shown in
Figs. 2(a) and 2(b) with Icomp of 10 μA and 500 μA,
respectively. It can be observed that all memristors are
initially at very low conductance states (∼1 × 10−7 mS).
© 2019 The Japan Society of Applied Physics
Appl. Phys. Express 12, 106504 (2019) Y. Wang et al.

(a) (b)

Fig. 1. (Color online) (a) The schematic diagram of the two-dimensional material MXene. (b) The schematic illustration of the Cu/MXene/SiO2/W
memristor device on the silicon substrate.

(a) (b)

(c) (d)

Fig. 2. (Color online) (a) and (b) Electroforming profiles of the memristor electroformed with the Icomp of 10 μA and 500 μA, respectively. (c) and (d) The
I–V curves of bidirectional DC voltage sweeping from −2.4 V to +2.4 V of the memristors electroformed with the Icomp of 10 μA and 500 μA, respectively.

After electroforming, the conductance states of memristors
increase to 0.002 mS and 0.5 mS for Icomp of 10 μA and
500 μA, respectively.27,28) It indicates that the increment of
the conductance states of the memristor after electroforming
has a clear positive correlation with the Icomp set during the
electroforming process. Then, the negative voltage was
applied to the devices to reset the memristor. Subsequently,
we applied a bidirectional DC voltage sweeping from −2.4 V
to +2.4 V for the electroformed memristors. Figures 2(c) and
2(d) show the I–V curves of set and reset process with Icomp
of 10 μA and 500 μA, respectively.
We can also observe that the changes in conductance of the
device electroformed with the Icomp of 500 μA is larger than
that of the devices electroformed with Icomp of 10 μA in both
electroforming process and set/reset process. The set and
reset I–V curves of memristor electroformed with smaller
Icomp (10 μA) have relatively distinct fluctuation. In contrast,
the curves of the memristor electroformed with larger Icomp
(500 μA) are comparatively smoother. In addition, the ratio
of Roff and Ron reading at 0.1 V of the memristor electro-
formed with the Icomp of 500 μA is about 20, while that of the
106504-2
memristor electroformed with the Icomp of 10 μA is about 4.
Thus, we can conclude that the magnitude of compliance
current set during electroforming process will directly
influence the following hysteresis characteristics of the
memristor.
From a biological point of view, short-term synaptic
plasticity is an important foundation for the function of
neural computation of biological synapses.29,30) During
the whole biological process, Ca2+ enter nerve endings
and trigger the rapid releases of neurotransmitters, which
induces instantaneous increase of the strength of synaptic
connections.31) PPF is a typical representation of short-term
synaptic plasticity.29,32) As shown in Fig. 3(a), during the first
stimulation, Ca2+ enter the presynaptic membrane through
Ca2+ channel. When the Ca2+ channel closed, the concen-
tration of Ca2+ reaches dynamic equilibrium, and the
existence of residual Ca2+ increase the concentration of
Ca2+ in the presynaptic membrane. When we apply the
second stimulation, the residual Ca2+ increase the release
probability of neurotransmitters, thereby enhancing the post-
synaptic responses.33,34) Similarly, we apply a pair of
© 2019 The Japan Society of Applied Physics
Appl. Phys. Express 12, 106504 (2019)
(a)
(b)
Fig. 3. (Color online) (a) The structural schematic of the signal transmission between synapses, and the diagram of the paired-pulse facilitation.
(b) and (c) The current responses of the paired pulses of memristors electroformed with Icomp of 10 μA and 500 μA, respectively.
presynaptic spike pulses to the memristor electroformed with
different compliance currents, the responses of the excitatory
postsynaptic current (EPSC) are shown in Figs. 3(b) and 3(c).
It is interesting to note that although the hysteresis curve of
memristor electroformed with small Icomp (10 μA) fluctuates
more obviously, the PPF index (the amplitude ratio of the
second EPSC to the first EPSC) is about 2.5, while that of
memristor electroformed with 500 μA is only about 1.3. We
can see that biological stimulus responses of the memristor
electroformed with smaller Icomp is clearly stronger than that
of the device electroformed with lager Icomp (500 μA).
Many studies have proved that the PPF index can be
adjusted by controlling the intervals between two spike
pulses.35) This phenomenon is considered as the feature of
the short-term synaptic plasticity, enabling neurons behave
flexibly enough in the execution of a series of computational
tasks, such as fundamental learning and information proces-
sing. We measured and calculated the PPF index under
different intervals, and plotted the functional curves between
PPF index and pulses intervals of memristor electroformed
with different compliance currents (the pulse intervals
increased by 10 ms in turn). As shown in Figs. 4(a) and
4(b), the PPF index of memristor electroformed with small
Icomp (10 μA) shows an exponential decrease trend with the
increase of pulse intervals, which can be well fitted by the
( )
formula y = A1 exp -Dtt + y0. The fitting curves are similar
1
to the authentic biological synaptic responses.36) While the
fitting curve obtained from the memristor electroformed with
larger Icomp (500 μA) measured under the same conditions is
almost a straight line with only small fluctuations.
106504-3
Y. Wang et al.
(c)
In addition, we also find that the memristor electroformed
with larger compliance current shows great analog behavior
and long-term plasticity. After electroforming process, we
applied successive negative and positive voltage sweep on
the devices electroformed with the Icomp of 500 μA. By
controlling the stopping voltage (1 V–2 V, each increased by
0.2 V in turn), we can obtain the analog I–V curves under
negative and positive sweep voltage respectively. As
Fig. 5(a) shows, there is almost no fluctuation or overlap
between each I–V loop. In addition to the voltage DC
sweeping, similarly to the LTD and LTP characteristics of
biological synapses,29,37) the conductance of the memristor
can also be modulated by successive spike pulses. We
applied a series of positive spike pulses (1.2 V, 20 ms) and
the negative spike pulses (−2.2 V, 20 ms) to the memristor.
As Fig. 5(b) shows, it is clear that the conductance of the
device increases or decreases gradually with the increase of
the number of corresponding positive and negative spike
pulses.
It is widely considered that the resistance change of
memristor is attributed to the formation and rupture of
conductive filaments induced by the redox reaction
of electrode and ionic transportation.38) We assume that
different compliance currents lead to different shapes of
conductive channel, and further affect biological character-
istics, such as short-term synaptic plasticity and long-term
plasticity. In Cu/MXene/SiO2/W memristor, the conductive
channel is mainly composed of Cu atoms. In the experiments,
the top electrode was oxidized: Cu → Cu2+ + 2e−. Under the
action of electric field, the Cu2+ gradually migrates to the
© 2019 The Japan Society of Applied Physics
Appl. Phys. Express 12, 106504 (2019)
(a)
Fig. 4. (Color online) (a) The fitting curves of the PPF index of memristors electroformed with Icomp of 10 μA. (b) The fitting curves of the PPF index of
memristors electroformed with Icomp of 500 μA.
(a)
Fig. 5. (Color online) (a) The analog I–V curves under negative and positive sweep for Icomp of 500 μA. (b) Long-term potentiation (LTP) and long-term
depression (LTD) under 50 positive spike pulses and 50 negative spike pulses alternately for Icomp of 500 μA.
Fig. 6. (Color online) (a) and (b) The schematic of the electroforming and
the extension of conductive channel with Icomp of 10 μA and 500 μA,
respectively.
bottom electrode (W), and is reduced to neutral atoms Cu,
generating conductive region from the bottom electrode to
the top electrode. When the Icomp of electroforming is
comparatively small, there exists a conical and unstable
conductive channel.17,39) During the first stimulation, the
106504-4
Y. Wang et al.
(b)
(b)
concentration of Cu near the bottom electrode is higher than
that of the top electrode. When the second stimulation is
applied, both the top and the bottom of the channel extend
laterally, therefore the current response of the second
stimulation is clearly larger than the first stimulation, as
shown in Fig. 6(a). When the Icomp is larger, two electrodes
are connected by a cylindrical conductive channel during the
first stimulation. As shown in Fig. 6(b), when we applied the
second stimulation, the lateral extending becomes saturated,
and the second current response is slightly larger than that of
the first one.39)
In this letter, we propose a memristor integrated with
MXene and reveal the manipulation of the compliance
current in electroforming process on the short-term plasti-
city and long-term plasticity of the memristor. By control-
ling the compliance current during electroforming process,
memristors may present different responses to the same
stimulation, such as bidirectional DC voltage sweeping and
paired pulse. In addition, we also find that the memristors
electroformed with large compliance current possess more
obvious long-term synaptic plasticity such as LTP/LTD.
This work would be meaningful for manipulating the
behavior of memristor and obtaining stable electronic
synapses; thus, providing effective guidance in promoting
the application of memristor in brain-inspired computing
systems.
Acknowledgments This work was supported in part by the National
Natural Science Foundation of China (Grant Nos. 61704088, 61874059,
61804079, and 21671167), the China Postdoctoral Science Foundation (Grant No.
2018M642290), the Jiangsu provincial key talent project (Grant Nos.
SZDG2018007 and TJ218001), and the NJUPTSF (Grant Nos. NY217116,
NY218110 and KFJJ20170101).
ORCID iDs Yuqi Wang https://orcid.org/0000-0003-1342-6804
© 2019 The Japan Society of Applied Physics
Appl. Phys. Express 12, 106504 (2019)
1) R. Mishra, D. Kumar, and H. Yang, Phys. Rev. Appl. 11, 054065 (2019).
2) V. Anggono and R. L. Huganir, Curr. Opin. Neurobiol. 22, 461 (2012).
3) N. K. Upadhyay, S. Joshi, and J. J. Yang, Sci China Inf Sci 59, 061404
(2016).
4) X. M. Zhang et al., IEEE Electron Device Lett. 39, 308 (2018).
5) X. Wan, F. Gao, X. J. Lian, X. C. Ji, E. T. Hu, L. He, Y. Tong, and
Y. F. Guo, Jpn. J. Appl. Phys. 57, 060303 (2018).
6) S. H. Jo, T. Chang, I. Ebong, B. B. Bhadviya, P. Mazumder, and W. Lu,
Nano Lett. 10, 1297 (2010).
7) H. Jeong and L. P. Shi, J. Phys. D: Appl. Phys. 52, 023003 (2019).
8) S. M. Yu, Proc. IEEE 106, 260 (2018).
9) P. M. Sheridan, F. X. Cai, C. Du, W. Ma, Z. Y. Zhang, and W. D. Lu, Nat.
Nanotechnol. 12, 784 (2017).
10) M. Hu et al., Adv. Mater. 30, 1705914 (2018).
11) A. Chanthbouala et al., Nat. Mater. 11, 860 (2012).
12) Y. Li, Y. Y. Kang, and X. Gong, IEEE Trans. Electron Devices 64, 4317
(2017).
13) Y. Li, K. Z. Han, Y. Y. Kang, E. Kong, and X. Gong, IEEE Electron Device
Lett. 39, 1211 (2018).
14) C. H. Pan, T. C. Chang, T. M. Tsai, K. C. Chang, T. J. Chu, P. H. Chen,
M. C. Chen, and S. M. Sze, Appl. Phys. Express. 9, 104201 (2016).
15) A. N. Mikhaylov et al., Mater. Sci. Eng. B-Adv. Funct. Solid-State Mater.
194, 48 (2015).
16) K. M. Kim, G. H. Kim, S. J. Song, J. Y. Seok, M. H. Lee, J. H. Yoon, and
C. S. Hwang, Nanotechnology 21, 305203 (2010).
17) C. H. Wang, W. He, Y. Tong, and R. Zhao, Sci. Rep. 6, 22970 (2016).
18) Z. Wang et al., Nat. Mater. 16, 101 (2017).
19) M. Khazaei, A. Ranjbar, M. Arai, and S. Yunoki, Phys. Rev. B: Condens.
Matter 94, 125152 (2016).
20) S. Lai, J. Jeon, S. K. Jang, J. Xu, Y. J. Choi, J. H. Park, E. Hwang, and
S. Lee, Nanoscale. 46, 19390 (2015).
106504-5
Y. Wang et al.
21) M. Khazaei, M. Arai, T. Sasaki, C. Y. Chung, N. S. Venkataramanan,
M. Estili, Y. Sakka, and Y. Kawazoe, Adv. Funct. Mater. 23, 2185 (2013).
22) T. Hu, J. M. Wang, H. Zhang, Z. J. Li, M. M. Hu, and X. H. Wang, Phys.
Chem. Chem. Phys. 17, 9997 (2015).
23) Q. Xue, H. Zhang, M. Zhu, Z. Pei, H. Li, Z. Wang, and S. Wang, Adv.
Mater. 29, 1604847 (2017).
24) X. B. Yan et al., Small 15, e1900107 (2019).
25) J. Liu, H. F. Yang, Y. Ji, Z. Y. Ma, K. J. Chen, X. X. Zhang, H. Zhang,
Y. Sun, X. F. Huang, and S. Oda, Nanotechnology 29, 415205 (2018).
26) T. W. Lee and J. H. Nickel, IEEE Electron Device Lett. 33, 1456 (2012).
27) O. Blazquez, J. L. Frieiro, J. Lopez-Vidrier, C. Guillaume, X. Portier,
C. Labbe, P. Sanchis, S. Hernandez., and B. Garrido, Appl. Phys. Lett. 113,
183502 (2018).
28) Z. W. Li, H. J. Liu, and X. Xu, Acta Phys. Sin. 62, 096401 (2013).
29) M. K. Kim and J. S. Lee, Acs Nano. 12, 1680 (2018).
30) S. Nadkarni, T. M. Bartol, C. F. Stevens, T. J. Sejnowski, and H. Levine,
Natl. Acad. Sci. USA. 109, 14657 (2012).
31) Q. J. Zhou et al., Nature 525, 62 (2015).
32) N. Tashiro and S. Nishi, Brain Res. 1672, 35 (2017).
33) Y. V. Medvedeva, M. S. Kim, and Y. M. Usachev, J. Neurosci. 28, 5295
(2008).
34) H. J. Jeong, I. S. Jang, A. J. Moorhouse, and N. Akaike, J. Physiol.-London.
550, 373 (2003).
35) P. Feng, W. W. Xu, Y. Yang, X. Wan, Y. Shi, Q. Wan, J. W. Zhao, and
Z. Cui, Adv. Funct. Mater. 27, 1604447 (2017).
36) X. B. Yan, J. H. Zhao, S. Liu, Z. Y. Zhou, Q. Liu, J. S. Chen, and X. Y. Liu,
Adv. Funct. Mater. 28, 1705320 (2018).
37) C. Pinar, C. J. Fontaine, P. J. Trivino, C. P. Lottenberg, M. J. Gil, and
B. R. Christie, Neurosci. Biobehav. Rev. 80, 394 (2017).
38) I. Valov, Chem. Electro. Chem. 1, 26 (2014).
39) K. M. Kim and C. S. Hwang, Appl. Phys. Lett. 94, 122109 (2009).
© 2019 The Japan Society of Applied Physics