Carbon 120 (2017) 54e62

Contents lists available at ScienceDirect

Carbon
journal homepage: www.elsevier.com/locate/carbon

Carbon nanowalls: A new material for resistive switching memory

devices
Paola Russo a, b, *, Ming Xiao a, b, Norman Y. Zhou a, b, **
a
Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L 3G1, Canada
b
Centre for Advanced Materials Joining, Department of Mechanical and Mechatronics Engineering, University of Waterloo, 200 University Avenue West,
Waterloo, Ontario N2L 3G1, Canada

a r t i c l e i n f o a b s t r a c t

Article history: In this work, we report for the first time the resistive switching behavior of a new type of device made of
Received 17 February 2017 carbon nanowalls (CNWs) deposited on fluorine-doped tin oxide (FTO) substrate. This new device shows
Received in revised form a forming-free bipolar resistive switching behavior, with a low operating voltage of 2 V and long
13 April 2017
retention time (5
10^4 s). The CNWs are synthesized by electrophoretic deposition of a solution of
Accepted 4 May 2017
Available online 7 May 2017
polyynes obtained by arc discharge. We show that the environmentally-friendly and time-saving fabri-
cation process we developed could overcome the current complex fabrication process of carbon-based
memory devices which impede their large-scale development. The obtained results demonstrate the
good reproducibility of the device's production process, and that the device's electrical performances can
be engineered with a control of the fabrication parameters. The study presented suggests that CNWs are
promising candidates for non-volatile memory devices and in carbon-based electronics.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction underlying resistive switching mechanisms in RRAM devices

depend on how the electron transport takes place in the sand-
Currently, much attention is being paid to resistive switching wiched structure, which can be attributed to a large variety of
random access memory (RRAM) devices as alternatives for the next physical and/or chemical phenomena. The mechanisms can be
generation of nonvolatile memories. The most common structure divided depending on whether the dominant contribution derives
of a RRAM device consists of an insulator/semiconductor layer from a thermal, an ionic or an electronic effect [21,22]. It has been
sandwiched between two metallic electrodes. The resistive widely demonstrated that the presence of lattice defects in the
switching (RS) behavior in this type of device is due to a resistance switching layer plays a key role in the resistive switching perfor-
change between high resistance state (HRS) and low resistance mance of the RRAM devices [22]. The most common resistive
state (LRS) when a voltage across the electrodes is applied [1e6]. switching mechanisms proposed in the current literature are: for-
Different types of RRAM have been fabricated based on the mation and rupture of conductive filaments induced by redox re-
different chemical composition of the insulator/semiconductor actions, Schottky emission, space-charge-limited conduction
layer and the different type of electrodes used. The materials that (SCLC) controlled by the presence of defects in the materials, i.e.
have been used for RRAM devices span from perovskites to tran- oxygen vacancies, that create charge-carrier traps, Pool-Frenkel
sition metal oxides such as TiO2, NiO, and ZnO to chalcogenides and emission, and trap-assisted tunneling where the RS originates
recently organic dielectric materials have been used [7e20]. The from the electronic charge injection and/or charge displacements
effects [1,3,4,21,23,24].
Carbon nanomaterials have been employed in a wide range of
* Corresponding author. Centre for Advanced Materials Joining, Department of applications, and it has been reported that tetrahedral amorphous
Mechanical and Mechatronics Engineering, University of Waterloo, 200 University carbon films, graphene oxide and carbon nanotubes show resistive
Avenue West, Waterloo, Ontario N2L 3G1, Canada.
switching behavior, opening the possibility for their application for
** Corresponding author. Centre for Advanced Materials Joining, Department of
Mechanical and Mechatronics Engineering, University of Waterloo, 200 University next-generation non-volatile memory devices [25e31]. Recently,
Avenue West, Waterloo, Ontario N2L 3G1, Canada. Ageev and coworkers published an interesting study on the resis-
E-mail addresses: [email protected] (P. Russo), [email protected] tive switching behavior of vertically aligned carbon nanotubes (VA
(N.Y. Zhou).

http://dx.doi.org/10.1016/j.carbon.2017.05.004
0008-6223/© 2017 Elsevier Ltd. All rights reserved.
 P. Russo et al. / Carbon 120 (2017) 54e62 55

CNT) under scanning tunneling microscopy (STM), induced by a electrodes during the electrophoretic deposition was kept at 5 mm.
distortion of the nanotubes upon the application of a voltage The FTO substrates, with a resistance of ~10 U sq1, before the
[29,32]. It was reported that the resistance ratio between the HRS polyynes deposition and fabrication of the CNWs, were cleaned in
and LRS was voltage dependent and reached 25 when 8 V was acetone, ethanol and isopropyl alcohol respectively and dried un-
applied to the STM probe/VA CNT. However, no further studies on der nitrogen gas flow. The CNWs deposition occurred at the cath-
the main electrical performance parameters (i.e. endurance, ode upon application of a voltage of 30 V at the electrodes for 1 h.
retention time) have been carried out on VA CNT. In this connec- The CNWs/FTO substrate was then annealed at 150  C for 1 h in
tion, carbon nanowalls (CNWs) are two-dimensional nanomaterials Argon gas, in order to remove the trapped water. In total three types
made of graphene layers that instead of being rolled up as in VA of heat treatments of the CNWs have been carried out: heat
CNT; they are vertically stacked onto a substrate leading to the treatment at 150  C in argon, in air and in argon followed by heat
formation of graphene “walls” [33]. These nanomaterials possess treatment in air.
the characteristic properties of graphene together with unique
characteristics induced by the presence of sharp edges and high 2.3. Fabrication of the memory device
surface area, which enable CNWs to be employed as field emitters,
catalyst support, capacitors and in Li-ion battery fabrication Al top electrodes with 100 nm thickness and 1 mm diameter
[34e39]. Moreover, it is well known that graphene-like systems were deposited by an e-beam evaporation process on the CNWs
possess high electrical conductivity along the basal plane, and the surface.
CNWs, due to their perpendicular orientation structure, possess an
enhanced electrical conductivity compared to graphene which 2.4. Characterizations
promises to be employed for devices fabrication [40]. To the best of
our knowledge no studies have been performed on whether CNWs Scanning Electron Microscopy (SEM) analyses have been per-
can be employed for the application of memory devices. In this formed using a ZEISS LEO 1550 FE-SEM at an accelerating voltage of
work, we report for the first time the resistive switching behavior of 5 kV. The X-ray photoelectron spectroscopy (XPS) analysis was
a new type of device made of CNWs on fluorine-doped tin oxide carried out using a multi-technique ultra-high vacuum imaging
(FTO) substrates. This Al/CNWs/FTO device shows a forming-free XPS microprobe spectrometer (Thermo VG Scientific ESCALab 250)
bipolar RS behavior, with a low operating voltage of 2 V and long with a monochromatic Al-Ka 1486.6 eV X-ray source. The spec-
retention time (5
104s). The study presented here, shows that trometer was calibrated by Au 4f7/2 (binding energy of 84.0 eV)
CNWs are promising candidates for the fabrication of non-volatile with respect to the Fermi level. The chamber vacuum level was
memory devices and their use in carbon-based electronics. In maintained below 2
1010 Torr. The carbon nanowalls were
particular, the environmentally friendly and time saving fabrication analyzed using a Renishaw In Via micro-Raman spectrometer,
process we developed could overcome the current complex fabri- employing an excitation laser with a wavelength of 633 nm, and the
cation process of carbon-based memory devices which impede spectra were acquired with a 50
objective at a laser power of
their large-scale development [41]. The results presented here 0.1 mW. HRTEM observation was conducted using a JEOL 2010F at
demonstrate the good reproducibility of the production process of the Canadian Centre for Electron Microscopy (Hamilton, Ontario,
the device, which electrical performances can be engineered with a Canada). TEM samples were prepared by scratching the samples
systematic control of the fabrication parameters. onto lacey carbon grids. Electrical measurements have been per-
formed with a Keithley 2602A source meter at ambient conditions.
2. Experimental
3. Results and discussion
The carbon nanowalls were obtained upon electrophoretic
deposition of a solution of polyynes, which are linear carbon chains The new CNWs-memory devices were fabricated in three steps
containing sp-carbon atoms [42]. The polyynes acted as building using arc discharge and electrophoretic deposition (EPD) for the
blocks for the fabrication of the carbon nanowalls and a similar synthesis and deposition of CNWs on FTO substrate, respectively.
fabrication method has been already published employing poly- Arc discharge in water of two graphite electrodes was employed for
ynes obtained by laser ablation of a graphite target and then the production of a solution of polyynes, which are linear carbon
deposited by electrophoresis [43]. The details about the synthesis of chains of sp-carbon atoms [42,44,45]. These nanomaterials were
polyynes and their EPD for the synthesis of the CNWs are given then used as building blocks for the synthesis of the CNWs; indeed
below. polyynes have a strong tendency to interchain crosslinking. The
EPD was used for the synthesis/deposition of CNWs on FTO sub-
2.1. Synthesis of the polyynes strate, since it has been demonstrated as an excellent method to
deposit carbon nanomaterials for forming free RRAM devices [47].
In this work the polyynes were obtained by arc discharge in FTO substrates were used as electrodes and immersed in the pol-
water between two graphite electrodes having a diameter of 10 mm yynes solution. Upon application of the electric field, the polyynes
and length 70 mm [42,44,45]. The arc discharge between the are transported at the cathode and undergo interchain crosslinking
electrodes was maintained for 10 min at a voltage of 30 V. In Fig. S1a reactions leading to the formation of hexagonal-graphene like sp2
picture of the arc discharge setup is displayed while in Fig. S2 is carbon structures perpendicular to the electrode's surface, i.e. the
shown the UV/VIS spectrum of the obtained polyynes. In particular CNWs [48,49]. After heat treatment in Argon at 150  C for 1 h, the
polyynes containing 6, 8 and 10 carbon atoms per chain were final step of the fabrication process was the deposition of Al top
produced [46]. electrodes on the CNWs/FTO substrate by e-beam evaporation. The
production method we developed is more user-friendly, cost-
2.2. Synthesis and deposition of the carbon nanowalls effective and eco-friendly compared to the current fabrication
methods employed for the synthesis of carbon-based electronic
The polyynes solution was transferred in a glass beaker and two devices, since no high temperatures or high pressures and
pieces of FTO/glass substrate were used as electrodes and sub- poisonous chemicals are needed [41]. Fig. 1a displays a schematic of
merged in the polyynes solution. The distance between the two the structure of the Al/CNWs/FTO devices fabricated, while in
56 P. Russo et al. / Carbon 120 (2017) 54e62

Fig. 1. (a) Schematic design of the structure of the Al/CNWs/FTO device, (b) schematic of the apparatus for the EPD of polyynes in order to obtain the CNWs. (A colour version of this
figure can be viewed online.)

Fig. 2. a) SEM image of the surface morphology of the CNWs prepared by EPD of polyynes. b) Magnification of the CNWs surface morphology. c) C1s XPS and (d) Raman spectrum of
the CNWs. (A colour version of this figure can be viewed online.)
 P. Russo et al. / Carbon 120 (2017) 54e62 57

Fig. 1b a schematic of the EPD process is displayed. The top-view fabrication of CNWs by EPD is crucial for the resistive switching
SEM image of the CNWs obtained after the EPD of polyynes on behavior of the device [21,22].
FTO substrate is shown in Fig. 2a which confirmed that the CNWs The CNWs were analyzed by Raman spectroscopy with an
are uniformly distributed over the substrate area. In Fig. 2b is dis- excitation wavelength of 633 nm and the relative spectrum is dis-
played the magnified SEM image of the CNWs. The SEM images played in Fig. 2d. It is possible to notice, that the Raman spectrum
show the typical morphology of the carbon nanowalls, where the obtained is the one characteristic of CNWs, as reported by Kurita
branched 2-dimensional carbon sheets are clearly shown. and Wang [52,53]. In particular, it can be observed the character-
Fig. 2c presents the C1s XPS spectrum of the electrophoretic istic D band originated by the presence of defects and the G band
fabricated CNWs. The C1s peak was fitted using a Gaussian- which arises from the in-plane vibration of sp2 carbon atoms. As
Lorentzian curve to four components in which the peak located at reported by Kurita [52], the narrow G band (~37 cm1) is due to the
284.35 eV indicates the presence of sp2 carbon atoms (C¼C), the presence of nanowalls made of small crystallites with high degree
peak at 285.04 eV is attributed to sp3 carbon atoms (C-C), while the of graphitization. In addition to these bands, a weak band is also
peaks at 286.03 eV and 287.87 eV can be ascribed to (C-OH) and observed corresponding to D0 band originated by the presence of
(-O-C¼O) groups respectively [43,50]. As shown in the inset in disorder. The length of the carbon nanowalls can be correlated to
Fig. 2c, the percentage of sp2 carbon atoms is 56.46%, while the ratio the ID/IG ratio, since it increases with decreasing the CNWs [52]. The
relative to sp3 carbon atoms is 19.01%, due to the presence of defect ID/IG ratio of the CNWs is 0.95 (see Fig. S3) and based on the liter-
sites or edges [51]. The presence of 10.34% of hydroxyl groups and ature the length of our CNWs should be around 1.8 mm [52]. It is
14.19% of (-O-C¼O) groups also suggest that a mild oxidation of the also reported that a decrease of the ID/IG ratio occurs upon addition
carbon nanowalls occurs during the fabrication process. The for- of O2 [53,54]. From Fig. 2b it is possible to notice that the CNWs are
mation of defects and presence of oxygen-containing groups upon smaller in length than 1.8 mm, therefore the low ID/IG ratio could be

Fig. 3. a) I-V curve of Al/CNWs/FTO device for first and 150 cycles of voltage sweeping. Arrows and numbers indicate the direction and sequence for the IeV scan. b) Endurance
results of the device for over 150 cycles at 0.4 V. c) Retention result over 5
104 s at a read voltage of 0.4 V. (A colour version of this figure can be viewed online.)
58 P. Russo et al. / Carbon 120 (2017) 54e62

attributed to the presence of oxygen groups which induce a mild period of 5
104 s, the currents for HRS and LRS, respectively
oxidation of the CNWs. From the TEM results displayed in Fig. S4 in measured at 0.4 V were stable, confirming the non-volatile nature
the Supplementary data it is possible to notice that, the CNWs are of the device.
made of 8e10 graphene layers with a d-spacing of 0.34 nm, which It is important to explore the origin of the RS effect in this new
is the interlayer distance in graphite. These results together with type of CNWs-based devices. Based on the type of the dielectric
the SEM and Raman analysis, confirm the synthesis of carbon layer sandwiched between the electrodes, the RS behavior has been
nanowalls. explained with different types of mechanisms [3,6,23]. In order to
The electrical performance of the fabricated Al/CNWs/FTO de- study the RS mechanism in our device, the I-V curves have been
vices was investigated by applying the sweep voltages of fitted to the different mechanisms and among them we found that
0 V / 2 V / 0 V / 2 V / 0 V. Fig. 3a demonstrates the typical the trap-controlled SCLC mechanism, which is controlled by the
bipolar resistive switching behavior of the new developed device presence of defects, best fit our device. The structural defects are
obtained under direct sweeping operations for 1 and 150 cycles. It related to the following mechanism for the formation of the CNWs
was found that the Al/CNWs/FTO device was initially in the LRS and upon EPD of polyynes. As aforementioned, polyynes are charac-
the device maintained this state during the voltage sweeping from terized by an extremely high reactivity with oxygen and a strong
0 to 2 V. The reason might be due to the dominance of sp2 carbon tendency to interchain crosslinking. Therefore, when polyynes are
atoms over the sp3, providing high conducting channels in the transported at the surface of electrode upon application of the
CNWs [55], as confirmed by XPS study in Fig. 2c. Moreover, as electric field, interchain crosslinking reactions occur leading to the
aforementioned, the vertical orientation of the CNWs parallel to the synthesis/deposition of CNWs [48,49]. The deposition process and
electrons flow causes a higher conductivity [40], leading to the the crosslinking reactions might lead to the formation of defective
initial LRS in our I-V current response. The device switches to the carbon structures (pentagon rings) with missing carbon atoms,
HRS during the voltage sweeping from 2 V to 0 V, which means that which results in the formation of defect sites in the CNWs. The
the RESET process occurs. The HRS remained after the negative presence of defect sites and oxygen is confirmed by the observation
voltage was applied until the negative voltage is high enough to of the peak at 285.04 eV attributed to sp3 carbon atoms (related to
transition the device from HRS to LRS. It should be noted that the the presence of defect sites) and the peaks at 286.03 eV and
resistive switching performance for our devices does not require 287.87 eV (related to oxygen containing carbon groups), as seen in
the commonly used electroforming step [55], desirable for the the XPS spectrum in Fig. 2c. Therefore, we hypothesize that due to
ReRAM devices due to the simplifying electrical operation. the presence of structural defects and oxygen in the CNWs, the RS
We have observed that the I-V curve obtained after 150 cycles is effect observed in our new device can be explained with the trap-
different from the one obtained after only one cycle and we hy- controlled SCLC mechanism. In order to verify this hypothesis, we
pothesize this could be attributed to a rearrangement of the oxygen replotted the I-V curves of the device heat treated in argon in
atoms in the CNWs structure induced by the first voltage sweep. double-logarithmic scale as shown in Fig. 4.
The reset and set currents slightly changed after the first cycle and The I-V curve characteristic of trap-controlled SCLC can be easily
stabilized with increasing the number of cycles. After 150 cycles it recognized since the HRS consists of three portions: (i) Ohmic re-
was still possible to distinguish the LRS and HRS, suggesting that gion (I f V) observed at low field; (ii) the Child's Law region (I f
this new type of device could be employed as RRAM in future V2); (iii) steep current increase observed at high field [23]. It can be
memory devices. The results of the cycling performance are shown seen that the I-V curves are in agreement with the trap-controlled
in Fig. 3b at the read voltage of 0.4 V. Over 150 cycles we found that SCLC mechanism. In particular, under positive voltage the LRS fol-
the difference between the LRS and HRS firstly decreased but the lows the Ohm's law conduction mechanism with a slope ~1, i.e.,
difference remained constant with increase in the number of cycles current varies linearly with applied voltage, while the HRS consists
probably as a consequence of the stabilization of CNWs structure, of two regions. At low voltage the current conduction follows the
suggesting a promising durability of the new device. Fig. 3c shows Ohm's law with a slope of ~1 and at higher voltage the Child's law
the retention results measured at room temperature. Over the time conduction mechanism is dominant, suggesting that the switching

Fig. 4. SCLC I-V characteristics of the Al/CNWs/FTO device plotted in double-logarithmic scale for the a) positive and b) negative bias. (A colour version of this figure can be viewed
online.)
 P. Russo et al. / Carbon 120 (2017) 54e62 59

Fig. 5. Schematic showing the RS mechanism of the Al/CNWs/FTO device. (a) The LRS after applying a positive bias. The electrons flow along the filled oxygen vacancies from the
bottom FTO electrode to the top Al electrode without the requirement of a forming step. (b) Transitioning from LRS to HRS caused by a de-trapping process of electrons from the
oxygen vacancies upon application of a negative bias. (A colour version of this figure can be viewed online.)

mechanism is controlled by the trap-controlled SCLC. The slope electrode without the requirement of a forming step. Upon the
value is lower than the one reported for the Child's law mechanism, application of negative bias, a de-trapping process of electrons from
however lower slope values have been recorded in case of conju- the oxygen vacancies occurs, which causes the device to transition
gated polymers and CNWs are made of conjugated carbon atoms from LRS to HRS. A schematic of the RS mechanism is shown in
[56]. Under negative voltage, the LRS was found to follow the Ohm's Fig. 5.
law, while the HRS showed three regions: at low voltage the con- These preliminary results indicated that the morphology of
duction mechanism followed the Ohm's law with a slope of 1. The CNWs plays a key role in the electrical performance of the device. In
intermediate region represents the transition between Ohm's and particular, we showed that the presence of defects sites, i.e. oxygen
Child's law conduction mechanisms [57]. The third region with vacancies, is vital for the RS behavior of the CNWs based devices.
slope 2.9 was seen to correspond to the Child's law region [57]. Therefore, it was of interest to try to engineer the concentrations of
From the above results we determined that the initial state of defects in the CNWs structure and study how the RS performance is
the device is LRS due to: (i) existence of defects sites, i.e. oxygen affected. Heat treatment of carbon nanomaterials is a way that can
vacancies, which act as trap centers for the electrons and (ii) the be employed for the modulation of oxygen containing groups [58],
perpendicular orientation of the CNWs on the FTO substrate which which might affect the RS behavior. Therefore, after 1 h of depo-
enhances the electrical conductivity. Therefore, upon the applica- sition of CNWs by EPD on FTO substrate, the substrate was heat
tion of a positive bias the electrons could flow along the filled ox- treated at 150  C in air at ambient pressure. The electrical perfor-
ygen vacancies from the bottom FTO electrode to the top Al mance was then investigated and compared to the sample heat

Fig. 6. a) Resistive switching characteristic after 1 and 20 cycles of the Al/CNWs/FTO device heat treated in air. b) C 1s XPS spectrum of the CNWs heat treated in air. (A colour
version of this figure can be viewed online.)
60 P. Russo et al. / Carbon 120 (2017) 54e62

Fig. 7. a) I-V characteristics after 1 and 20 cycles at a sweeping voltage of 2 V. b) retention of the device at 0.2 V. c) XPS spectrum of C 1s. (A colour version of this figure can be
viewed online.)

treated in argon at 150  C. In Fig. 6 are shown the I-V characteristics restoration of the sp2 hybridization and a decrease in the oxygen
of the device heat treated in air under the voltage sweep of 2 V. containing groups. The heat treatment in air leads to more
Fig. 6a shows that the RS behavior is similar to the device heat conductive and less defective CNWs in term of oxygen containing
treated in argon, with the device initially in the LRS state. Note- groups compared to the CNWs heat treated in argon and this could
worthy, the LRS/HRS ratio after one voltage sweep at 2 V was higher be the reason for the instability of the device. In particular, as
for the sample heat treated in air than the one heat treated in argon aforementioned, the presence of defects, i.e. oxygen vacancies,
(LRS/HRS of 7 and 3 respectively at the read voltage of 0.4 V); plays a key role in the RS behavior of our device and the fact that the
however, the device did not show a good endurability. In particular, heat treatment in air led to CNWs with less content of oxygen and
after few cycles the device became unstable and the LRS and HRS higher content of sp2 carbon atoms might affect the RS behavior.
became undistinguishable, as displayed in Fig. 6a. Clearly, this This result leads us to the hypothesis that the fabrication of CNWs
demonstrates that the heat treatment conditions after the deposi- with a smaller percentage of sp2 carbon atoms and higher per-
tion process play a key role in the stability of the device. The reason centage of oxygen containing carbon groups could lead to more
for the instability of the device might be the presence of a higher stable devices [55]. In order to confirm our hypothesis a pre-
percentage of sp2 carbon atoms and a lower percentage of oxygen liminary experiment was carried out with heat treatment of the
containing carbon groups after the treatment in air atmosphere. In CNWs first in argon, in order to remove the trapped water mole-
Fig. 6b the XPS spectrum of C1s is displayed together with the cules, followed by heat treatment in air at 150  C. In Fig. 7a, the I-V
atomic percentages (inset) of carbon atoms and carbon groups characteristics after sweeping a voltage of 2 V for 1 cycle and after
detected in the sample. It was found that compared to the XPS 20 cycles are displayed. We noticed that after one cycle the LRS/HRS
spectrum of the sample heat treated in argon (Fig. 2c), in the ratio reached a value of 9, however the device was not very stable
sample treated in air the percentage of sp2 carbon atoms increased and after few cycles the LRS and HRS collapsed. The retention
by ~ 24%, while the percentage of hydroxyl groups and carboxyl experiment carried out at a voltage of 0.2 V showed that the device
groups were 7.54% and 4.42%, respectively. This result suggests, was able to maintain the LRS and HRS up to 2000 s with a ratio of
supported by the current literature, that the heat treatment in air at ~10. Compared to the device heat treated only in argon and only in
150  C induced a reduction of the CNWs [59], leading to a air, we found that the new type of heat treatment increased the
 P. Russo et al. / Carbon 120 (2017) 54e62 61

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