Aerosol Jet Printed WSe2 Based RRAM on Kapton

Suitable for Flexible Monolithic Memory Integration

Yida Li, Maheswari Sivan, Jessie Xuhua Niu, Hasita Veluri, Evgeny Zamburg, Jinfeng Leong, Umesh Chand, Subhranu Samanta,
Xinghua Wang, Xuewei Feng, Yunshan Zhao, and Aaron Voon-Yew Thean
Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3,
Singapore 117583
li.yida@nus.edu.sg, Aaron.Thean@nus.edu.sg

elusive. Here, we described the process of a first fully printed

I. ABSTRACT room temperature WSe2 RRAMs on flexible kapton substrate
In this work, we demonstrate the first fully printed WSe2 using AJ technology, with a cell size of ~70 x 70 µm2. Our
resistive random access memory (RRAM) fabricated using results demonstrates potential for the printed flexible RRAM to
aerosol jet printing approach from few layers WSe2 suspended be used in conformal electronics applications.
solution at room temperature on flexible kapton substrate. The
printed WSe2 RRAM exhibits forming free, unipolar behaviour, III. RESULTS AND METHODOLOGY
sub 1-V switching voltage, 2 orders high resistance state A. WSe2 based RRAM Fabrication Process
(HRS)/low resistance state (LRS) ratio, and large LRS retention
The WSe2 RRAM is constructed in a two-terminal vertical
time > 2.5 hours. Furthermore, the WSe2 RRAM exhibits both
metal/insulator/metal (MIM) structure, utilization Ag or CNT as
volatile and non-volatile switching behaviour with a transition
the top/bottom metal. The printing is done on Kapton using a
set current of 2 µA. In addition, the WSe2 RRAM retains its
high-precision AJ printing method (Optomec AJ5X). We use
functionality even after flexing down to a bending-radii of 5 cm,
WSe2 ink consisting of few layers flakes suspended in ethanol
thus showing suitability for its use as embedded memory in
(concentration 0.1 mg/ml, from 2D Semiconductor). During
conformal electronics system.
printing, the ink is ultrasonically atomized into fine mist
II. INTRODUCTION continuously and carried out using N2 carrier gas [13]. The
bottom and top electrodes – Ag (Clariant) or CNT (Sigma
Flexible electronics has been gaining significant attention for Aldrich) are printed via the pneumatic atomizer. The printed Ag
its potential to be utilized in applications that requires non- lines are transformed into conductive state by a localized 830
conformal surface attachment such as wearables.[1-3] A number nm laser sintering process to drive off the binder, while the
of materials including both organics and inorganics has been printed CNT requires no further process. Table I shows the
studied for their use in flexible thin-film-transistors (TFT) detailed printing parameters used in this work, while Figure 1
logics.[4-7] In order to complement the flexible logics, there is (a) - (c) shows the schematic and photo image of a 2 x 2 WSe2
a need to search for novel flexible memory. Conventional RRAM array, as well as the zoomed in microscopic image of the
transition metal oxides (TMO) pose a challenge due to its fabricated Ag RRAM devices respectively. The RRAM cell size
brittleness. Novel 2D transition metal dichalcogenide (TMD) as is limited to the width of the printed electrodes, which in this
a RRAM material is shown to exhibit good switching case, is 70 x 70 µm for Ag, and 80 x 80 µm for CNT.
characteristics, flexible, and can be solution processed for
printing.[8-14] At the large scale flexible electronics TABLE I. PRINTING PARAMETERS USED
manufacturing, the printing approach is a promising technology
considering the low thermal budget and complexity required for Printing Steps
Nozzle Sheath Carrier Line
flexible substrates integration. Aerosol jet (AJ) printing is an Size Flow Flow Width
emerging printing technology that boast features such as on the Ag electrodes (PA*) –
fly ink mixing/atomization and handling inks over wide range of Laser sintered at 100 300 µm 60 sccm 30 sccm 70 µm
mW, speed = 10 mm/s
viscosity.[15] For realization of memory on flexible substrates,
solution processed novel materials and printing technology are CNT electrodes (PA*) 300 µm 50 sccm 25 sccm 80 µm
essential technology enablers. WSe2 layer (UA*) 300 µm 50 sccm 35 sccm 80 µm
In previous reports, researchers has looked into the use of *UA – Ultrasonic atomizer, PA – Pneumatic atomizer
various 2D layered materials (eg. hBN, MoS2) as a RRAM
medium, utilizing the intrinsic materials defect for resistive
switching.[12-13] However, these devices are not able to be
scaled up to large volume. The closest demonstration of a larger
scale fabrication is from a solution based MoOx/MoS2 RRAM
using a spin coating approach and using printed Ag as the metal
electrodes on a PEN substrate, but is still inadequate.[11] A
directed printing approach of the required materials is a better Fig. 1: (a) Schematic of a 2x2 RRAM array, (b) photo image of the flexible
solution. In addition, the use of other TMDs in RRAM remains 2x2 WSe2-RRAM array, and (c) microscopic image of the WSe2 RRAM with
Ag electrodes (70 µm line width),

978-1-5386-9304-9/19/$31.00 ©2019 IEEE

B. Material Characterization found to be volatile for 500 nA set current, i.e. the RRAM
Fig 2 (a) shows the SEM image of the WSe2 layer, while Fig returns to HRS from the LRS as soon as the bias is removed.
2 (b) and (c) show the average thickness vs number of printing However, when the set current is increased to 2 µA, the Ag-
passes, and the corresponding microscopic images respectively. WSe2 RRAM becomes non-volatile, and exhibits a unipolar
Due to the low concentration of WSe2 in the ink, we print the behaviour with a reset voltage/current in the region of 0.3 V/80
WSe2 layer over 30 passes (~300 nm average thickness) to avoid µA (Fig. 4 (c)), translating to an operating power of 2.4 µW. At
shorts between the top/bottom electrodes. The morphology of its stable LRS, the retention time is tested to be > 2.5 hours at
the as-printed WSe2 layer is highly disordered with random room temperature, and a HRS/LRS resistance ratio of ~2 orders.
orientation of the material, significantly different from typically Furthermore, there appears to be no degradation in performance
exfoliated WSe2 flakes. of the WSe2 RRAM after flexing down to a bending radii of 5
cm. Table II shows the benchmark table of the printed WSe2
RRAM with reported RRAMs on flexible substrates.
a)(a) 500 Set Current = 500 nA b) 500
400 400
300 300
200 200
100 100

I (nA)

I (nA)
0 0

-100 -100

-200 -200

-300
-300
Set for positive V -400
-400
Set for negative V
-500
-500
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
-1.0 -0.5 0.0 0.5 1.0
V (V)
V (V)

c) d)(f)
10-4 108 HRS
HRS
Set
10-5 reset

Resistance (Ohm)
7
10
I (A) 10-6
106
10-7
Fig. 2: (a) SEM image of the printed WSe2 layers, (b) Thickness vs 105
Number of printing passes relationship, and (c) microscopic image of the
10-8 LRS
LRS

10-9
printed WSe2 layer with different number of printing passes indicated 104

10-10
In Fig. 3 (a), the Raman spectroscopy plot shows that the in 0.0 0.2 0.4 0.6 0.8 1.0
103
100 101 102 103 104
plane, E2g mode of the printed WSe2 layer is consistent with the Voltage (V) Time (s)

exfoliated bulk WSe2. The absence of interlayer coupling B2g Fig. 4: DC sweep of WSe2 RRAM with (a) Ag electrodes at set current of 500
mode, and out of plane, A1g mode is likely due to the disordered nA, (b) CNT electrodes at set current of 500 nA, (c) Ag electrodes at set current
arrangement of the printed WSe2. In addition, the low-angle X- of 2 µ, and (d) retention curve of the WSe2 RRAM
Ray diffraction (XRD) spectroscopy shown in Fig. 3 (b) shows
the various phases of WSe2 confirmed the random orientation of TABLE II. BENCHMARKOF RRAMS ON FLEXIBLE SUBSTRATES

the printed WSe2, correlating with the SEM image in Fig. 2 (a).
Set Reset
Structure Method Scalability
Voltage Voltage
Normalized Raman intensity

1.0
Ag/WSe2/Ag
a) E2g1
b)
WSe2 exfoliated 400
& transferred Fully AJ printed 0.7 V 0.3 V Yes
0.8
WSe2 ink printed (this work)
Intensity (A.U.)

300
Ag/MoOx/MoS2/Ag Printing +
0.6 A1g 1V 1V No
200
[11] spincoating
0.4 Semiconductor
Ni/NiOx/Ti/Pt [16] -4.2 V 3V No
0.2
B2g 100 process
Semiconductor
0
0.0 Al/TiO2/Al [10] process on -2 3 No
75 150 225 300 375 450 30 40 50 60 70 80 90
kapton
Raman shift (cm ) -1 Theta (θ)
Semiconductor
Cu/WO3-x/ITO [17] 1 -1.1 No
process on PET
Fig. 3: (a) Raman spectroscopy, and (b) low angle XRD spectroscopy of the
printed WSe2 layer on kapton D. Conclusion
C. Electrical Characterization In summary, we have demonstrated a fully printed WSe2
DC sweep of the printed WSe2 RRAM is done with a set based RRAM on flexible substrate using a room temperature AJ
current of 500 nA (Fig. 4 (a) and (b) for Ag and CNT electrodes printing process. The printed RRAM exhibits lower switching
respectively). The directions of the hysteresis cycle sweep is voltage and operating power compared to similar flexible
indicated by the arrows. The device exhibits a forming free RRAM. By varying the set current of the printed RRAM,
switching behaviour, and can be set in both positive and negative volatile/non-volatile behavior can be achieved. The printed
polarity bias. The abrupt switching of both RRAMs at sub 1-V RRAM retains its functionality even after flexing down to a
suggests the switching due to filamentary based conduction, in bending-radii of 5 cm, making it suitable to be monolithic
agreement with reported work.[12] The smaller switching integrated as embedded memory in conformal electronics.
voltage could indicate a more defective printed WSe2 layer, but
requires further investigation. The switching characteristic is
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Acknowledgements
The work is supported in part by Singapore’s National Research
Foundation, Hybrid Integrated Flexible Electronic Systems
(HiFES) Program (hifes.nus.edu.sg), and E6Nanofab at the
National University of Singapore (NUS).