2012 12th IEEE International Conference on Nanotechnology (IEEE- NANO)

The International Conference Centre Birmingham

20-23 August 20112, Birmingham, United Kingdom

Nanosensors Based on Graphene Inter-layer Electronic Properties:

Sensing Mechanism and Selectivity

Fubo Rao, Member, IEEE, Haider Almumen, Wen Li*, Member, IEEE, and Lixin Dong*, Senior
Member, IEEE

Ahstract- Graphene-based nanosensors with inter-layer which can potentially achieve higher sensItIvItIes of
structures were built and tested as gas sensors in response to graphene based nanosensors. The inter-layer graphene
ethanol and water molecules, and were compared with intra­ nanosensor primarily uses the inter-layer electronic
layer nanosensors built on mono-layer and bi-Iayer graphenes.
properties instead of the intra-layer electronic properties of
Ethanol and water molecules were chosen because they act
differently as donors and acceptors to graphenes. The results
the graphene, as schematically shown in Fig. 1. The
show that the sensitivities of the inter-layer graphene principle of the inter-layer structured graphene nanodevice
nanosensors were over two times higher than the ones based on was demonstrated by fabricating electrodes on two different
the mono-layer and bi-Iayer graphenes under the same layers of the bi-layer graphene so that the electrical
experimental conditions. Strong suppression of the tunneling transduction through the two graphene sheets can be
current through the two stacked graphene layers was observed,
exposed. Several inter-layer graphene nanosensors and intra­
which is mainly caused by the reconstruction of the microscopic
corrugation due to the adsorption of gas molecules.
layer ones based on mono-layer or bi-Iayer graphenes were
fabricated with nanofabrication technologies and
Index Terms - Graphene, nanosensors, inter-layer, hi-layer, characterized as gas molecule sensors in order to study their
mono-layer. sensing effects. Two types of gas molecules, ethanol and
water, were investigated for testing sensor responses because
I. INTRODUCTION they act differently as donors or acceptors to graphenes [3].
s a typical two-dimensional nanomaterial, graphene The results show that the sensitivities of the inter-layer

A has, in recent years, drawn significant attentions to

scientific community because of its attractive
nanosensors were more than two times higher compared to
the nanosensors based on either mono-layer graphenes or bi­
electronic, physical and optical properties and a wide variety layer graphenes under the same experimental conditions.
of promising applications [1, 2]. For example, graphene­ Strong suppression of the tunneling current was observed,
based nanosensors have been reported, which can detect the which is mainly caused by the reconstruction of the
attachment or detachment of single gas molecules [3]. A lot microscopic corrugation due to the adsorption of gas
of nanodevices based on graphenes, from mono-layer to molecules. Our development of inter-layer graphene sensors
few-layer structures, have been constructed and evaluated by provides a different technique to make nanosensors with
different groups [4]. Most nanodevices, however, are higher performance for detecting various stimuli such as
fabricated on the top layers of the graphene films and utilize chemical/biological molecules and forces, and significantly
the intra-layer electronic properties. Less attention has been enriches the applicable transduction mechanisms in
paid to the inter-layer electronic properties between two graphenes.
stacked graphene sheets due to the difficulties in structuring
exposed inter-layer steps in graphenes. The merits of this
exposure include inter-layer tunneling, doping and other
effects besides the enhanced edge effects due to the extra
sides. Inter-layer effects can be a function of the spacing
change caused by molecule adsorption/desorption,
force/displacement, pressure, surface tension or thermal
energy, and thus can potentially enrich the applicable
transduction mechanisms in sensing. All these effects will be
Fig. I Schematic cartoon shows the structure of a nanosensor based on
available only if electrical contacts can be made on different the inter-layer electronic properties of graphenes.
layers of a graphene.
In this paper, we reported an inter-layer graphene concept,
II. METHODS

All authors are with the Department of Electrical & Computer
Engineering, Michigan State University, East Lansing, MI 48824 USA.
(Corresponding authors: Wen Li, e-mail: wenli@egr.msu.edu; Lixin Dong,
email: Idong@egr.msu.edu ).
Graphene based nanosensors were fabricated with
nanofabrication techniques. Graphene samples were first
prepared with mechanical exfoliation from highly oriented
pyrolytic graphite (HOPG) flakes and then transferred on the

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 Si02 (300 nm)/Si substrates prior to nanofabrication introducing water vapor to the vacuum chamber. The
processes. The 300 nm thick Si02 was chosen to make pressure of water vapor was maintained to a constant value
mono-fbi-layer graphenes visible under an optical of 500 Pa in the vacuum chamber during the test. The
microscope [5]. After locating the graphene sheets on the sensing behavior of the devices was characterized by
substrate, Raman spectroscopy was used to further identify measuring transduction currents through constantly biased
their thickness based on the characteristics of the G and the intra-layer and inter-layer graphene sensors using Keithley
second-order Raman 2D bands [6, 7]. A graphene trimming 6487 picoammeter and HP 4145B semiconductor parameter
technique based on oxygen plasma etching [8] was used to analyzer.
cut graphenes to more regular shapes. After that, graphene
samples were subjected to an annealing process in an ArIH2 III. RESULTS
environment to clean the graphene surfaces before being
V=O.01 V
processed for device fabrication.
2.7
(a)
The device fabrication processes for both intra-layer and ...... ....,.--nI_�
... .....,

inter-layer structured graphene sensors are schematically

depicted in Fig. 2. Electrodes (5 nm Tif80 nrn Au) were
selectively fabricated on the same (Fig. 2a) or different (Fig.
2b) graphene layers through electron-beam lithography,
metal thermal evaporation and lift-off processes.
After the fabrication processes, another annealing process 2.3
in the ArIH2 environment was applied to the fmished devices
in order to remove possible contaminations and form better Electrode 1&2

o 40 80 120
ohm-contacts between electrodes and graphene surfaces.
Time (s)
(b)
(a) V=0.01V
____iiiiiiiiiiiiiiiiii
iiii
ii __
ii.

0.5

� 0.4
C
l!!
:;
() 0.3

(b)
0.2
Electrode 2&3

100 200 300 400 500

Time (s)

Fig. 3 Current responses of (a) the mono-layer graphene sensor, and (b)
the inter-layer graphene sensor to ethanol molecules. A gas mixture of
• • 0.5% ethanol (volume) and nitrogen was introduced to the test system
I S1 layer graphene 2nd layer graphene for creating an ethanol environment The inset in (a) shows the SEM
image of the device which includes a mono-layer graphene sensor
(formed between electrodes 1 and 2) and an inter-layer graphene sensor
• (formed between electrodes 2 and 3) on a same graphene. The arrows
Sial Au show the time when ethanol molecules were introduced to the test
system. Scale bar is 2 11m.

Fig. 2 Schematic processes for fabricating (a) intra-layer and (b) inter­
sheet structured graphene nanosensors.
Both intra-layer and inter-layer structured graphene-based
nanosensors were tested to study their responses to ethanol
and water molecules respectively. The device sensing
responses to ethanol molecules were studied at room
temperature using a custom-designed fluidic set-up, as
described in our previous paper [9], by introducing 0.5%
(volume) ethanol in nitrogen backfill. The device responses
to water molecules were measured at room temperature in a
scanning electron microscope (SEM, Zeiss EVO LS25) by
Typical responses of the graphene based nanosensors to
the 0.5% ethanol in nitrogen are shown in Fig. 3. As shown
in the inset SEM image of Fig. 3, the graphene had both a
mono-layer region and a bi-layer region. The mono-layer
region A and the bi-layer region B were identified with
Raman spectroscopy. An inter-layer graphene nanosensor
and a mono-layer one were intentionally fabricated on a
same graphene sample. The inset SEM image shows that the
formation of the inter-layer nanosensor between electrodes 2
and 3 and the intra-layer nanosensor between electrodes 1
and 2.

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 The graphene nanosensors were characterized by in response to the absorption of water molecules is shown in
measuring current responses through different pairs of Fig. 4. It can be seen that a dramatic decrease of the inter­
electrodes, with an applied bias of 0.01 V to avoid Joule layer current was observed when water molecules were
heating damage and electrical breakdown of graphenes. The introduced to the test system. A slow recovery of the inter­
response curve of the intra-layer nanosensor (Fig. 3a) layer current was also observed when the water vapor supply
displayed a current increase from 2.2 fJA in the nitrogen was turned off. It can be attributed to the slow desorption of
environment to 2.67 fJA in the 0.5% ethanol environment, the water molecules from the graphene surfaces at room
resulting in a normalized resistance change (L'lRlR) of temperature. This recovering time can be significantly
28.3%, where L'lR was measured resistance change due to the reduced by heating the device to increase the speed of
introduction of ethanol and R was the baseline resistance of desorption.
the device. The response curve of the inter-layer nanosensor
(Fig. 3b) shows a current decrease from 0.55 fJA in the (a)
1.76
V=7.5mV
nitrogen environment to 0.22 fJA in the 0.5% ethanol
environment, resulting in an L'lRlR of 59.6%, which is more
than twice the sensitivity of inter-layer device. ,..... 1.72
<t:
Inter-layer nanosensor was also constructed and tested .:;,
upon exposure to water molecules, and was compared with -
c:: 1 .6 8
ones built on the mono-layer and the bi-Iayer graphenes. The �
::J
inset of Fig. 4 shows the SEM images of an inter-layer U 1.64
nanosensor by fabricating Ti/Au electrodes on a graphene
consisting of both a mono-layer region 1 and a bi-Iayer 1 .60 �,
�,
region 2. The mono-layer and bi-Iayer graphene regions
were identified with Raman spectroscopy. 0 400 800 1200 1600
Time (s)
(b)
1.80
iL.....1r<1I"'1II.I 2.48
V=2mV
.--.. 1.76 2.44 ..
<1:!
.6 <-
'E 1.72 .6
-
2.40
� c::

�
8 1.68 ...
::J
2.36
u
1.64 2.32

o 400 800 2.28

600
Time
0 1200 1800 2400
(s)
(c) Time (s)
Fig. 4 Current response of the inter-layer nanosensor upon exposure to 2.00
water molecules with a pressure of 500 Pa in the test system. The black
arrow indicates the time when the water vapor was introduced into the V=4mV
test system and the red arrow indicates the time when the water vapor
was vacuumed from the test system. The inset shows the SEM images 1.96 ..
of the inter-layer nanosensor. The scale bar is 311m. <-
.6
'E 1.92
!!!
....
The water vapor responses of the above-mentioned intra­ ::J
layer and inter-layer sensors were characterized in the SEM
U 1.88
chamber. During the experiments, the sample chamber was
first pumped to a base pressure of less than 3.3 x 10-3 Pa in
order to remove possibly absorbed vapor molecules on the �
1.84+-�-,--�-,-,--.-�-,--.-�
graphene surfaces of the sensors. Then, water vapor was o 400 800 1200 1600 2000
introduced into the sample chamber and the pressure inside Time (s)
the sample chamber was maintained at 500 Pa. After several
minutes, the water vapor source was turned off and the Fig. 5 (a), (b) and (c) show the current responses of the inter-layer,
mono-layer and the bi-Iayer structured nanosensors under several
sample chamber was pumped down again to the base cycles of water molecule turning ON and OFF, respectively. The black
pressure. The current response of the inter-layer nanosensor arrows indicate the time when the water vapor was introduced into the
test system and the red arrows indicate the time when the water vapor

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 was vacuumed from the test system. The insets in (b) and (c) show the
SEM images of the mono-layer graphene nanosensor and the bi-Iayer
graphene nanosensor, respectively. The scale bars in the insets of (b)
and (c) are 311m and 1 .511m, respectively.
Several cycles of water vapor supply turning ON and OFF
were also applied to the intra-layer and inter-layer
nanosensors and the results were displayed in Fig. 5. The
insets of Fig. 5 (b) and (c) show the SEM images of intra­
layer nanosensors fabricated on a mono-layer graphene and
a bi-Iayer graphene, respectively. The mono-layer and bi­
layer graphenes were also confIrmed with their Raman
spectra. Fig. 5 (a)-(c) show the current responses of the
inter-layer nanosensor and the intra-layer ones based on
mono-layer and bi-Iayer graphene in several test cycles. The
L1R1R values of the nanosensors achieved from the response
curves indicated that the L1R1R of the nanosensors fabricated
on the mono-layer graphene and the bi-Iayer graphene were
4.6% and 4.8%, respectively, while the L1R!R of the inter­
layer nanosensor was 9.8% which is also twice the responses
of intra-layer nanosensors under the same test conditions.
The data are consistent with results obtained in the above
ethanol sensing experiments.
The higher sensitivities achieved from the inter-layer
nanosensors can be attributed to the strong exponential
relationship between the tunneling current through the two
adjacent graphene layers and the inter-layer distance, due to
the absorption of ethanol or water molecules. It is also
noticed that the resistance of the inter-layer nanosensor
increased no matter whether the introduced gas molecules
are donors (ethanol) or acceptors (water), as shown in Fig.
3(b) and 5(a). These results indicate that the inter-layer
nanosensor exhibits a different sensing mechanism
compared to the intra-layer nanosensors. Although the exact
sensing mechanism of such inter-layer structured devices
needs further investigations, we believe that the current
tunneling through the top and the bottom graphene layers
plays an important role that contributes to the higher
sensitivities.
IV. CONCLUSION
This paper reports a graphene-based nanoscale sensor
with an inter-layer confIguration, which has been
demonstrated to have higher sensitivities than the common
intra-layer sensors. Intra-layer and inter-layer sensors were
fabricated on different mono-layer and bi-Iayer graphenes,
and also on the same graphene. The devices were tested as
molecule sensors upon exposure to ethanol and water vapor
molecules. The advantages of using the inter-sheet graphene
as a sensing element were demonstrated by the signifIcant
enhancement of the sensitivity. When being exposed to the
donor-type gas molecules (0.5% ethanol in nitrogen), 59.6%
normalized resistance change was achieved from the inter­
layer sensor while only 28.3% normalized resistance
changes was measured from the intra-layer sensor. When
being exposed to the acceptor-type gas molecules (500 Pa
water vapor in a vacuum chamber), the inter-layer sensor
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showed a normalized resistance change of 9.8%, while the
intra-layer sensors based on the mono-layer graphene and
the bi-Iayer graphene showed only 4.6% and 4.8%
normalized resistance changes, respectively. There is a high
likelihood that this sensitivity improvement has been
attributed to the suppression of the tunneling current through
the top and bottom layers of the graphene due to the
adsorption of vapor molecules, either mechanically by
surface-tension-induced distortion or electronically by inter­
sheet electron donation. These inter-layer effects
signifIcantly enrich the applicable transduction mechanisms
and provide a promising candidate for sensing various
stimuli, such as chemical/biological molecules,
force/displacement, pressure and surface tension with high
sensitivities.
ACKNOWLEDGMENT
This work was carried out mainly in the W. M. Keck
Microfabrication Facility at Michigan State University. The
authors would also like to thank Dr. Baokang Bi and Mr.
Brian Wright for assistance with experiments and helpful
discussions.
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