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Graphene oxide-based flexible metalinsulatormetal capacitors

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2013 Semicond. Sci. Technol. 28 055002
(http://iopscience.iop.org/0268-1242/28/5/055002)
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IOP PUBLISHING

SEMICONDUCTOR SCIENCE AND TECHNOLOGY

doi:10.1088/0268-1242/28/5/055002

Semicond. Sci. Technol. 28 (2013) 055002 (7pp)

Graphene oxide-based flexible


metalinsulatormetal capacitors
A Bag, M K Hota 1 , S Mallik and C K Maiti
VLSI Engineering Laboratory, Department of Electronics and ECE, Indian Institute of Technology,
Kharagpur, 721302, India
E-mail: mksan21@gmail.com

Received 11 December 2012, in final form 1 March 2013


Published 28 March 2013
Online at stacks.iop.org/SST/28/055002
Abstract
This work explores the fabrication of graphene oxide (GO)-based metalinsulatormetal
(MIM) capacitors on flexible polyethylene terephthalate (PET) substrates. Electrical properties
are studied in detail. A high capacitance density of 4 fF m2 measured at 1 MHz and
permittivity of 6 have been obtained. A low voltage coefficient of capacitance, VCC-, and a
low dielectric loss tangent indicate the potential of GO-based MIM capacitors for RF
applications. The constant voltage stressing study has shown a high reliability against
degradation up to a projected period of 10 years. Degradation in capacitance of the devices on
flexible substrates has been studied by bending radius down to 1 cm even up to 6000 times of
repeated bending.
(Some figures may appear in colour only in the online journal)

1. Introduction

in applications where the ability to deform is an advantage


or where they should preferably take the shape of the object
into which they are being integrated [14]. Flexible electronics
technology opens up new possibilities in applications such as
flat panel displays, solar cells, radio frequency identification
(RFID) tags, low cost sensors and other disposable electronic
devices [15]. In this regard, graphene-based flexible devices
are found to be promising [16]. However, the main challenge
in flexible electronics is how to maintain the integrity
of the circuits during and after flexing or stretching the
substrate.
In this study, GO films have been drop-cast on ITO-coated
polyethylene terephthalate (PET) substrates to evaluate the
possibility of the fabrication of flexible MIM capacitors with
GO as an insulator. The physico-chemical properties of GO
films on PET/ITO substrates are elucidated by studying the
chemical bonding states and surface morphology using Fourier
transform infrared attenuated total reflectance (FTIR-ATR)
spectra and atomic force microscopy (AFM), respectively.
Quantitative capacitancevoltage (CV) measurements of
flexible MIM capacitors are performed to evaluate electrical
parameters such as voltage linearity, dielectric characteristics,
dissipation factor and the effect of electrical stressing. Flexible
capacitors on PET substrates were repeatedly (>6000 times)
bent to 1 cm bending radius for the flexibility test.

In recent years, researchers have started taking serious interest


in all carbon electronics due to their unique mechanical
and other electronic properties which can overcome many
technological challenges currently being faced by the
conventional silicon electronics [17]. Among various carbonbased materials, ultrathin graphene oxide (GO) is very
promising due to its unique physico-chemical properties; for
example, with its water solubility, GO can be transferred
onto any substrates uniformly using simple methods such as
drop casting. The as-deposited GO thin films can further be
processed into functional devices using standard lithography
processes without degrading the film properties leading to
fabrication of large-scale flexible, transparent and printable
devices [811]. GO normally consists of oxygen functional
groups, such as epoxide, hydroxyl and carboxyl groups, on
their basal planes and edges. With a wide band gap (6 eV) and
a reasonable dielectric constant, GO is also very promising for
metalinsulatormetal (MIM) capacitor applications [1213].
A particular area where GO-based MIM capacitors are
required is in the field of flexible electronics.
Flexible electronics are becoming popular due to their
potential low cost and light weight, and they are very useful
1

Author to whom any correspondence should be addressed.

0268-1242/13/055002+07$33.00

2013 IOP Publishing Ltd

Printed in the UK & the USA

Semicond. Sci. Technol. 28 (2013) 055002

A Bag et al

2. Experimental details
We used ITO-coated PET as flexible substrates for the
fabrication of GO-based MIM capacitors. The ITO-coated
PET film was purchased from Sigma-Aldrich. The surface
resistivity of the ITO is 60 /sq. and the thickness of
the ITO is 100 nm. Initially, the substrates were cleaned
sequentially with acetone and methanol in an ultrasonic
bath for about 5 min followed by DI water rinse. In this
work, ITO not only acts as the bottom electrode, but the
lower part also acts as a good adhesive layer with the
PET substrates. The GO layer was formed by the drop
casting method. The GO in aqueous solution (0.1 mg ml1)
was obtained from Nanocs Inc., USA (product: GO1-AQ-1,
graphene oxide, aqueous solution, 20 ml). However, before GO
layer formation, the ITO-coated PET substrate was exposed
to UV light for 1.5 h for better adhesion of GO. The
GO film thickness was measured by a surface profilometer
(Veeco Dektak 150) at five locations for three different
samples, and the average thickness of the film was found as
370 nm. Finally, as the top electrode, Pt was deposited by
dc sputtering in Ar ambient through a shadow mask (area
1.96 103 cm2). The CV measurements were performed
using an Agilent E4980A precision LCR meter. Before
CV measurements, open and short correction was carried
out to remove the parasitic series resistance and capacitance.
The constant current stressing (CCS) and constant voltage
stressing (CVS) were employed using an Agilent 4156C
semiconductor parameter analyser. Periodically, the stressing
and CV measurements were performed by switching the
measuring instruments automatically by an Agilent E5250A
low switching mainframe through a computer programming
controlled system.

Figure 1. Fourier transform infrared-attenuated total reflectance


(FTIR-ATR) spectra of graphene oxide (GO) films on the
ITO-coated PET substrate.
Table 1. List of roughness values obtained from the flexibility study
for GO film, ITO and Pt.
Materials
under test
Bottom electrode (ITO)
Graphene oxide
Top electrode (Pt)

Flexibility

RMS value of
roughness, Rq (nm)

Before
After
Before
After
Before
After

12.28
13.05
23.43
30.59
20.09
25.53

1
3
5
7
4
5

3. Results and discussion


of flex, the AFM study was performed. An AFM (NanoSurf
EasyScan 2) was used in non-contact mode (Si3N4 tip) with
a scanning area of 5 m 5 m. We measured at multiple
locations for better accuracy, before and after 6000 times flex
for studying the surface morphology of the bottom electrode
(ITO), GO film and top electrode (Pt). Three combinations,
PET/ITO, PET/ITO/GO and PET/ITO/GO/Pt, were used
during the flexibility study of ITO, GO film and Pt layers,
respectively. For each sample, we used five different locations
and extracted the root mean square (RMS) roughness (Rq).
The extracted values are shown in table 1. It may be observed
that the roughness value increases after 6000 times flexibility
test for all the three materials. Figures 2(a) and (b) show the
surface morphology of the GO films on PET/ITO before
and after 6000 times flex, respectively. It is observed that
the RMS value of the roughness increases from 23 to
30 nm after being bent 6000 times. Similar changes are
also observed for the top and bottom electrodes, as shown in
figures 2(c)( f ). However, the bottom electrode (ITO) shows
more stability under the flexibility text and hence is a suitable
electrode material for flexible device applications. However,
the increase in roughness value for the GO films and top
electrode (Pt) is more. Moreover, the performance of ITO

3.1 Material characterization


3.1.1. FTIR-ATR spectra. The structural analysis of the GO
film was performed using FTIR-ATR spectroscopy (Agilent
Cary 630) in the wave number ranging from 3200 to 700 cm1,
as shown in figure 1. The most prominent peak observed in
the spectrum of GO at 1733 cm1 is due to the presence
of C=O carbonyl stretching. Other observed peaks are at
1367 cm1 for COO symmetric stretching, at 1226 cm1 for
COH stretching (presumably from phenols), at 1053 cm1 for
CO stretching and at 829 cm1 for CH out-of-plane wag.
Several researchers have reported similar functional groups in
GO film [17, 18]. It is significant that the presence of addends
other than carboxylic acid groups verifies the heterogeneous
property of the GO films. Moreover, FTIR-ATR spectra
provided the evidence of the presence of different types of
oxygen functionalities in the GO films. The presence of the
multiple oxygen-bearing addends signifies the complex nonstoichiometric property of the GO film.
3.1.2. Atomic force microscopy analysis. In order to
understand the surface morphology after several hundreds
2

Semicond. Sci. Technol. 28 (2013) 055002

A Bag et al

(a)

(b)

(c)

(d )

(e)

(f)

Figure 2. Surface morphology study of the GO film, bottom electrode (ITO) and top electrode (Pt) during the flexibility study. Surface
condition of the GO, ITO and Pt before ((a), (c) and (e) respectively) and after 6000 times flexibility study ((b), (d) and ( f ) respectively).

and GO films in a PET/ITO/GO/Pt multilayer might have


changed slightly during the flexibility study. During the AFM
study, the top surface of the ITO and GO films was uncovered.
Indeed, the increase in roughness is likely due to the growth
of micro cracks caused by mechanical stress. However, it
may be noted that the GO films can sustain even thousands
of flex.

3.2. Electrical characterization


3.2.1. CV nonlinearity. CV linearity is considered the most
important parameter for MIM capacitors used for analogue/RF
applications. It depends on various parameters such as the
material properties of the insulator, top and bottom electrodes,
measuring frequency, metal electrodedielectric interface,
physical thickness of the dielectric, etc [1922]. Figure 3 shows
3

Semicond. Sci. Technol. 28 (2013) 055002

A Bag et al

Figure 4. Variation of the dynamic dielectric constant and loss


tangent as a function of the applied bias.

Figure 3. Capacitancevoltage nonlinearity as a function of


different applied frequencies.

the CV nonlinearity at different frequencies of ITO/GO/Pt


MIM capacitor structures. It is found that the CV nonlinearity
decreases with increasing frequency. The capacitance of the
MIM capacitors can be described by the following polynomial
relationship:
C(V ) = C0 (V 2 + V + 1),

(1)

where and are the quadratic and linear voltage coefficient


of capacitance (VCC) and C0 is the zero-bias capacitance.
By plotting and fitting C(= C(V ) C0 )/C0 versus V with
experimental data, one can obtain the VCC- and VCC-.
According to the ITRS roadmap, both the VCC values should
be less than 100 [23]. However, the linear VCC value can
be cancelled out by proper circuit design [24]. Therefore,
the quadratic VCC is the most important MIM capacitor
parameter for analogue circuit applications. The origin of the
CV nonlinearity can be explained by the dielectric dipole
polarization (P), which leads to the dielectric permittivity
through the following relationship [25]:
V
(2)
P = 0 (r 1) ,
td
where r and td are, respectively, the relative dielectric
permittivity and the physical thickness of the GO film
used in MIM capacitors. The capacitance is correlated to
the dielectric permittivity and consequently to the electrical
susceptibility, which is actually originated from the electric
dipole polarization following equation (2). Thus, the parabolic
dependence of the MIM capacitance on voltage is observed.
Next, to obtain the dielectric permittivity, the conventional
parallel-plate capacitor relation is used. The variation of the
dielectric permittivity is shown in figure 4. It is observed that
the dielectric permittivity is almost constant in the applied
bias range and its average value was found to be 6.0. The
dielectric loss tangent was found to be less than 1 (see figure 4),
which is acceptable for MIM capacitor applications. The
dielectric loss was calculated using the following relationship
[26]:
G( f )
,
(3)
tan =
2 fC( f )

Figure 5. Change in capacitance density with applied frequency.


Variation of the quadratic VCC as a function of the applied
frequency (inset).

where G( f ) and C( f ) are the conductivity and capacitance


respectively, measured at a fixed frequency, f . However, a
small variation in both the dielectric permittivity and dielectric
loss tangent was observed. The origin of such variations
may be due to the influence of the finite resistance of the
electrodes, leaky grain boundaries and the presence of a barrier
layer between the insulating film and the electrode surface
[27]. These results justify the nonlinear nature of the MIM
capacitors.
3.2.2. Capacitance frequency nonlinearity. The frequency
response of the capacitance is important for MIM capacitors,
especially in mixed signal circuit applications. Figure 5 shows
the zero-bias capacitance as a function of the measurement
frequency. The nonlinearity in capacitance density with
applied frequency has also been observed. Large frequency
dispersion (63%) has been observed in the applied frequency
range. In addition, it has also been observed that the
VCC- value decreases with increasing frequency (inset of
4

Semicond. Sci. Technol. 28 (2013) 055002

A Bag et al

Figure 7. Dependence of extrapolated C/C0 after a 10 year stress


under constant voltage stressing (5 and 7 V).

Figure 6. Relative capacitance change under injected fluences after


constant current stressing (CCS).

dielectric permittivity and the trapped charge is given by [30]

figure 5). It may be due to the existence of the large charge traps
at the electrodeGO interface. Since different traps exhibit
different time constants, it is reasonable to expect that as the
frequency increases, fewer traps will be able to follow the
ac signal and hence a decrease in measured capacitance was
observed. Generally, the frequency dependence of quadratic
VCC implies a strong relationship with the relaxation time in
the GO layer. This frequency dispersion may also be due to the
electrode polarization effect. By electrode polarization, mobile
carriers form an accumulation layer at the electrodes, leading
to a voltage-dependent double layer capacitance, which can be
expressed as follows [28, 29]:


AD
C = Cm 1 +
,
(4)
1 + 2 2

2
8 q2
h 8 q
+
N
,
(5)
d3Ke
d3Kh
where q is the unit charge, d is the distance between the
molecules, is the atomic polarizability of the dielectric and
Ke/Kh and Ne/Nh are the potential energy profile of the trap
(spring constant) and the density of the trapped charges inside
the dielectric for the electron and the hole, respectively [31].
Thus, it may be concluded that the oxide-trapped charges
increase the local permittivity, leading to an increase in the
capacitance.
To further investigate the degradation mechanisms of
the GO-based MIM capacitors, the CVS was carried out
with different constant voltages. The effects of CVS on the
dielectric properties were evaluated by alternatively switching
CVS and CV measurements which allowed an investigation
into the stress-induced degradation exclusively for the GO
layer. Figure 7 shows that the capacitance increases with
stress time under different CVS measured at 1 MHz. The
change of capacitance occurs due to the charge trapping effect
between the GO film and the electrode. These traps affect
charge trapping of carriers in the dielectric materials, and
trapped carriers can generate new dipoles, which results in an
increase in capacitance density as a function of stress time,
and higher stress voltage can cause more charge trapping
at deep traps [32, 33]. Figure 7 shows the extrapolated
C/C0 for a 10 year lifetime as a function of the different
stress voltages. The good reliability characteristic with a small
C/C0 of less than 1.0% was obtained. The logarithmic
increase of C/C0 also signifies the voltage nonlinearity
in the capacitance characteristics as discussed above. This
nonlinearity may be due to the creation of oxygen vacancies
after stressing.

= GO + N e

where Cm is the capacitance in the absence of electrode


polarization, is the corresponding relaxation time constant
and AD is the Debye length correction parameter. The
nonlinearity factor decreases at high frequencies for a fixed
bias and hence the capacitance decreases with increasing
applied frequency. It is clear that the nonlinearity of MIM
capacitors is related to the presence of a double layer
capacitance, electrode nature and also the oxygen vacancies.
3.2.3. Constant current and voltage stressing effects. To
determine the degradation mechanism in GO-based MIM
capacitors, CCS measurements were carried out. The relative
capacitance variation (Cs C0 )/C0 as a function of the
injected charge at room temperature (300 K) for two different
constant current values (40 and 60 A) is shown in figure 6. It
is observed that the relative capacitance variation increases
logarithmically with the injected charges, which implies a
correlation between the capacitance variation and the charge
trapping in the GO film. The capacitance of MIM capacitors
is directly proportional to the dielectric permittivity of the GO
layer which is also related to the trapped charge generated
during the constant current stressing. The relation between the

3.2.4. Flexibility study on capacitance. In order to confirm


the feasibility of GO-based MIM capacitors for flexible
electronic applications, mechanical flexibility tests were
5

Semicond. Sci. Technol. 28 (2013) 055002

A Bag et al

depend on a number of factors such as substrate modulus,


film adhesion and film cohesion [35]. The most common
failure modes for fragile films on flexible substrates are film
cracking/channelling and debonding [36].

4. Conclusion
The objective of this work has been the evaluation and
feasibility study of fabricating graphene oxide-based MIM
capacitors for flexible electronic applications in which
reliability is the primary concern. In this study, a GO thin film
on plastic substrates was prepared successfully with the drop
casting method. The results of detailed physico-chemical and
electrical properties of GO thin films on flexible substrates
for possible flexible electronic applications are reported.
Acceptable capacitance density with low VCC- and a low
loss tangent was obtained. However, high frequency dispersion
in capacitance and VCC- has been observed. The relative
capacitance increases logarithmically as a result of both the
CCS and CVS. The origin of this increase may be related
to the oxygen vacancies and/or oxygen interstitials, which
may be formed after electrical stressing. Finally, the GO films
show reasonable mechanical flexibility in a repetitive bending
test owing to their high ductility and the low-temperature
process used. The process developed in this work may provide
a practical approach for the fabrication of flexible MIM
capacitors using GO.

Figure 8. Capacitance degradation under mechanical flexibility


tests. Radius of curvature effect on capacitance density (inset).

performed along with the curvature test and its effect on


the capacitance was measured. The most important issue for
a flexible electronic application is that different layers in the
device should be stable even after several thousand flex. The
GO-based MIM devices used in this study are of cylindrical
shape. It is accepted that the outer surface experiences more
stress compared to the inner surface during the curvature test.
The collapsing radius test is the most common technique for
this type of bend test, while recently a more sophisticated
technique called the XY test has been developed [34].
However, for the sake of simplicity, we used the bend test
in this study. The flexibility test of the plastic device was
performed with the help of an automatic mechanical vibrator.
The details of the experimental setup can be found in our
previous report [14]. To understand the bending effects on
capacitance, devices were bent with the help of a different
curved surface having a different radius of curvature, and
the corresponding capacitance values were measured during
bending. The capacitance variation with different radii of
curvature is shown in the inset of figure 8. It is observed
that the capacitance remains almost unchanged during the
bending test. However, the capacitance value measured with
the bending of radius of curvature of 10.43 mm increases
a little bit. During the bending of the flexible devices, the
area of the capacitor increases due to the Poisson effect on
PET and the dielectric thickness may also be reduced. As a
result, the capacitance values increase. These results suggest
that GO-based devices may be suitable for flexible electronic
applications where bending of the circuit is necessary.
The capacitance density degradation with several flexes
is shown in figure 8. It is observed that after 700 flexes the
capacitance degrades by almost 44% of the initial capacitance
value; however, after that the degradation rate decreases
and after 6000 times bending, 40% degradation was found.
Moreover, it is worth noting that the failure modes of layered
materials usually involve the growth of micro cracks under
mechanical stress. However, the details of the fracture mode

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