Proceedings of the 15th

IEEE International Conference on Nanotechnology

July 27-30, 2015, Rome, Italy

ZnO nanowire-F
FET for charge-based seensing of
prootein biomolecules
1,2
N.M.J. Ditshego, 1N.A.B. Ghazali,, 1M. Ebert, 1K. Sun, 1I. Zeimpekis, 1,2P. Ashburn, 1,2M.R.R.
M de Planque,
1,2
H.M.H. Chong
1
Nano Research Group, Electroniccs and Computer Science, Faculty of Physical Sciences an
nd Engineering,
Universityy of Southampton, Southampton SO17 1BJ, U. K.
2
Member of IEEE.
Email: nm
mjd104@ecs.soton.ac.uk, hmhc@ecs.soton.ac.uk

Abstract — Top-down method was used d to fabricate zinc

oxide (ZnO) nanowire field effect tran nsistor (NWFET)
biosensor. The nanosensor was used to meassure the electrical
characteristics of lysozyme (LYSO) and bovin ne serum albumin
(BSA) protein solutions in phosphate buffeered saline (PBS).
The LYSO and BSA proteins are oppossitely charged at
measurement pH of 7.4. Subthreshold voltagge shift of 340 mV
and 700 mV due to surface charge effect on tthe device channel
is obtained for the LYSO and BSA solution ns respectively. A
NWFET sensitivity of 72 % is achieved for th he LYSO proteins
while the BSA proteins resulted in a sensitivityy of 98%.

Keywords— zinc oxide, field effect trannsistor, nanowire,

device, nanosensor, lysozyme (LYSO), phosphaate buffered saline
(PBS), bovine serum albumin (BSA)

I. INTRODUCTION
Zinc Oxide (ZnO) nanowire field eeffect transistors
(NWFETs) have recently attracted attentionn in chemical and
biosensing applications [1]–[3]. The semiconducting
property of ZnO has been exploited and haas led to different
fabrication methods of ZnO nanowiress sensor design
configurations and electrical performancces. The sensing
mechanism of the NWFET is based on the interaction of the
conducting channel to the presence of surface charges
introduced in liquid or gaseous state [4]–[66]. The advantage
of the NWFET is the possibility of direct, real-time and
label-free detection of molecules. In adddition, electrical
sensitivity of the NWFET can be improvedd by the nanowire
size which has a large surface area to vvolume ratio and
comparable to most biological entities [7], [[8].
There has been much work done onn bottom-up ZnO
nanowires sensors [7], [9], [10]. These senssors possess good
electrical characteristics but their orientaation, dimensions
and wafer scale addressability can be challeenging to achieve.
Top-down nanowire fabrication methhod has been
demonstrated in silicon [10] but little work has been done in
ZnO material. Previous top-down ZnO nnanowire work is
based on low cost photolithography, confformal deposition
and anisotropic etching method. It haad shown good
fabrication control of the dimension and location on the
wafer [11]. The pre-determined orientationn and position on
the substrate enable the nanowires to bee configured into
functional sensing device. In this work, we characterized the
performance of a low temperature fabricateed top-down ZnO
NWFET device in the presence of PBS bufffer solution,
Fig. 1. ZnO NWFET device structure (a) andd (b) Optical microscope
images; (c) image derived from scanning elecctron micrograph (SEM). The
device has channel length of 20 μm, width 20
0 nm and thickness 120 nm.
without or with the negatively charrged protein BSA or the
positively charged protein LYSO O. These proteins were
selected because they are ofteen used in biosensor
development studies. The NWFET T switching operation is
based on depletion mode because of the naturally n-type
ZnO channel. The electrical meassurement focuses on the
charge effect of the LYSO and BSA B acting on the ZnO
nanowire subthreshold region. Sub bthreshold voltage shift
from the proteins can be used to extract the charge
sensitivity, determine protein chargge polarity and estimate
the charge distribution. From the sub
bthreshold characteristics
of the ZnO NWFET channel arraay, we observed a large
voltage shift due to the charges of the
t proteins and compare
well with our simulation model.. The low temperature
fabrication process can be transferrred to low cost substrate
such as glass or plastic.
II. EXPERIME
ENT
Fig. 1 (a) and (b) shows the top
p view microscope image
of the 100 nanowires FET biosenssor with the source and
drain aluminium contacts. Fig. 1(c)) shows the image of the
ZnO nanowire using scanning elecctron micrograph (SEM).
Fabrication process starts with a 150 mm diameter p-type Si
wafer and a 300 nm thick layer off thermally grown SiO2.
The nanowire spacer template is first formed by
photolithography pattern transfer and
a reactive ion etching

978-1-4673-8156-7/15/$31.00 © 2015 IEEE 801

(RIE) of the SiO2 using CHF3 gas chem mistry. The RIE
produced a SiO2 trench depth of 120 nm deep and 10 μm
wide. Then remote plasma atomic layer depposition (RPALD)
is used to put a layer of 76 nm ZnO onto tthe surface of the
SiO2.

Fig. 4. Measured subthreshold IDS -VGS plot of

o PBS, LYSO, BSA.

Fig. 2. Schematic cross section diagram of the biosensoor having a 20 μm x The device was measured subssequently in air, in pure-
120 nm x 20 nm. The ZnO donor concentration is 1.7 x 1018 cm-3. PBS solution, in LYSO solution in BSA B solution, and finally
in air again over a period of 6 hours.h Fig. 3 shows the
Anisotropic inductively coupled plasm ma (ICP) etcher electrical characteristics of the devicce in air. Fig. 3(a) and (b)
and CHF3 gas chemistry is then used to remove the ZnO shows clear linear, pinch-off, and saturation regions with
layer. The ZnO thickness at the edge of thhe SiO2 spacer is threshold voltage of -5.50 V. Thee NWFET has a drain
approximately twice the thickness to the flaat surface. Due to current on/off ratio of 107 and su ubthreshold slope of 1.0
the thicker ZnO at the spacer sidewall areea, only the non- V/decade. Fig. 3(b) is the subthreshold and linear IDSVGS
spacer flat surface region is fully etched ouut. The remaining plot of the NWFET in air beforee being exposed to the
ZnO will form the nanowire channel. The advantage of this analytes (denoted as AirBefore) and d air after exposure to the
method is the maskless approach and the naanowires are self- analytes (denoted as AirAfter). Fig g. 4 shows the measured
aligned to the source and drain, as shown inn the Fig. 1 and 2. electrical characteristics of the prottein solutions. It shows a
Then thermal ALD is used to deposit a passivation layer of distinct subthreshold voltage shift between the BSA and
18 nm thick Al2O3 over the ZnO nanowiress at a temperature LYSO solution. The pure-PBS solution is used as a
of 200 oC. Aluminium lift-off process then forms the ohmic reference voltage to determine the subthreshold
s voltage shift
contacts at the source and drain region. Finnally, SU-8 resist for the BSA and LYSO at fix xed IDS = 1 nA. The
is pattern on top of the device to form a sennsing well for the subthreshold voltage shift obtained d for LYSO and BSA is
bioanalytes. Fig. 2 shows the schematic crooss section of the 340 mV and 700 mV respectively. The T negative voltage shift
sensor with the NWFET and SU8 well. Soluutions used in the of the LYSO indicates nanowire surface association of a
experiment are: phosphate buffered saline (PBS) (150 μM positive charged molecule and the positive voltage shift of
NaCl, 10 μM phosphate, pH 7.4), chiicken egg white the BSA signifies surface associatio on of a negative charged
lysozyme in PBS (LYSO) and bovine serum m albumin (BSA) molecule, in accordance with the expected charge of the
in PBS, with LYSO or BSA concentrationss of 0.5 μM. The LYSO and BSA proteins at pH 7..4. After the bioanalytes
device underwent multiple rinses in DII water between measurement, the NWFET is able to o return to its original air
measurement of the protein and pure-PBS solutions. state electrical characteristic as show
wn in Fig. 3 (b).

II. RESULTS AND DISCUSSIION Table 1. Measurement of device sensitivity

Sensitivity
Subthreshold
ǻI
ǻ from fixed
ǻV from fixed % Sensitivity
VGS = -9 V
IDS = 1nA
LYSO 350 mV 5.2 nA 72 %

BSA 700 mV 1.9 nA 98 %

Table 1 shows subthreshold vo oltage shift of LYSO and

BSA with reference to PBS. The chaange in output current IDS
is derived from a fixed gate vo oltage of -9.00 V. The
Fig. 3. (a) IDSVDS characteristics with a VGS drive from -10 V till 10 V with
steps of 2.0 V (b) IDSVGS characteristics of air before (bblack) and after (red)
sensitivity of detection calculation is based on the change of
measuring analyte solutions. conductance in the nanowire under bias due to the influence
of the protein charges [12], [13]. Sensitivity
S of 72.0 % for
the LYSO protein solution and 98.0 0 % for the BSA protein
solution has been achieved. These values
v are in comparison

802
to silicon based NWFET sensor, if not highher. The state-of-
the-art voltage shift is between 200 mV andd 300 mV [14].
We used a commercial software calledd Silvaco [15] to
model the effect of surface charge of the pprotein molecules
on the NWFET. Fig. 5 shows the structure w which is assumed
to have single crystal (single grain) ZnO channel with the
same physical parameters as the fabricatedd device. RPALD
tends to deposit crystalline and uniformly ddoped ZnO layer;
therefore a uniform doping profile and a single grain is
assumed. The bulk ZnO layer is assumed tto be defect-free;
all defects are incorporated at the insulator--channel interface
and within the insulator [15]. The reasonn for assuming a
defect-free ZnO crystal is to investigatte the effect of
subthreshold voltage shift. A neutral block-llayer is placed on
top of the Al2O3 representing biomolecular ssolutions.
Fig. 5. 2D structure of the simulated ZnO biosensor deerived from tonyplot.
On top of the Al2O3 is a ‘neutral block-layer’ that repreesents analyte
solutions.
Fig. 6. Subthreshold IDSVGS graph: 2D simulation comppared with
experimental results of PBS measurement.
Fig. 6 shows a good fit between experiment and
simulation. Both simulation and the experimmental curve have
subthreshold slope of 1.0 V/decade, on/off current ratio of 1
x 107. These are values derived at VDS = 12.0 V. The analyte
fixed charge (QAF) is derived from simulattion to be 1.19 x
10-7 C.cm-2. This value will be used as referrence to calculate
803
the difference in charge introduced d to the NWFET model.
Fig. 7 shows that by increasing or decreasing the QAF, it
causes a subthreshold voltage shift to the left or right. The
analyte fixed charge was increased to 1.26 x 10-7 C.cm-2 so
as to fit LYSO results. This produced a voltage shift of 300
mV which is comparable to experiiment. The difference in
charge represents the effective LYSO O charge per unit area on
the surface of the channel given by y 0.70 x 10-8 C.cm-2. The
analyte fixed charge is then decreassed to 1.08 x 10-7 C.cm-2
so as to fit the BSA results. This produced a voltage shift of
700 mV which is comparable to experiment. The difference
in charge represents the effective BSA
B charge per unit area
b 1.10 x 10-8 C.cm-2.
on the surface of the channel given by
Fig. 7. Subthreshold IDSVGS simulation plot of PBS, LYSO, BSA. It shows
that positive analyte fix charge shifts voltage to the left while negative
charge shifts to the right.
The subthreshold voltage shift due to the protein charges is
further verified using Equation 1, which is the depletion
mode threshold voltage equation foor the ZnO NWFET. The
equation accounts for all charge deefects in the insulator, at
the insulator/ZnO interface, at thhe surface and also the
accumulation charge. It is used to t verify the simulation
results concerning the analyte fixeed charge for the LYSO
and BSA proteins. Table 2 explainss the symbols used in the
equation.
ܳ஺ி ൅ ܳூ் ‫ܰݍ‬஽ ݀ ଶ ͳ ʹ‫ ݍ‬ଶ ݀ ଶ ܰ஽ଶ
்ܸு ൌ െ െ െ ඨ (1)
‫ܥ‬௢ ߝ௓௡ை ߝ௢ ‫ܥ‬௢௫ ߝ௓௡ை
From the measured PBS thresh hold voltage of -5.50 V,
the QAF is calculated to be 2.45 x 10 0-7 C.cm-2. The measured
LYSO threshold voltage of -5.85 V has QAF of 2.52 x 10-7
C.cm-2. Finally, the QAF value off 2.30 x 10-7 C.cm-2 is
obtained from the BSA threshold voltagev of -4.80 V. The
analyte fixed charge difference betw ween PBS and LYSO is
0.70 x 10-8 C.cm-2, which is equiv valent to the simulation
results. The charge per unit area diffference between PBS and
BSA is 1.50 x 10-8 C.cm-2, whicch is comparable to the
simulated value of 1.10 x 10-8 C.cm-2 -
. The good match of the
simulated and measured subthresho old characteristics of the
 NWFET suggests the presence of associated fixed charges of
the proteins, which is also observed in [12]-[14].
Table 2. Symbols clarified for equation 1.
Parameter Value
CNW Oxide capacitance (F) for a single nanowire = 0.76 fF
Cox Oxide capacitance per unit area = 21.1 nF/cm2
QIT Interface state charge (C.cm-2)
-2
QAF Analyte fixed charge (C.cm )
R Radius of the nanowire = 60 nm
Gate oxide thickness under NW + nanowire radius (R)
t Lett., vol. 85, no. 26, pp. 6389–6391, Dec. 2004.
of nanowire = 240 nm
ࢿ࢕ Permittivity in vacuum (8.85 x 10-14 F/cm)
ࢿࢆ࢔ࡻ Effective dielectric constant for ZnO nanowire (8.66)
CONCLUSION
High sensitivity ZnO NWFET biosensor has been
fabricated and measured. A sensitivity of 72.0 % for LYSO
protein solution and 98.0 % for BSA protein solution in PBS
buffer has been achieved. Under different analytes
environment, the device produces a stable subthreshold
slope of 1.0 V/decade, which is suitable for charge sensing.
The electrical characteristic of the NWFET is able to return
to its original state after exposure to analyte solutions.
Successful 2D simulation and analytical calculation were
used to obtain the charge per unit area and identify the
positive charged LYSO and negative charged BSA protein.
The results compared well to the measured subthreshold
voltage shift of both proteins. The high sensitivity of the
ZnO NWFET sensor can be exploited for selective analyte
detection by functionalizing the nanowire surface with
antibodies or other biomolecular probe molecules.
ACKNOWLEDGMENT
N.M.J. Ditshego would like to acknowledge the
Botswana International University of Science and
Technology (BIUST) for supporting his doctoral studies and
the Southampton Nanofabrication Centre for the
experimental work. The authors would like to acknowledge
EPSRC EP/K502327/1 grant support.
N.A.B. Ghazali would like to acknowledge the
Universiti Sains Malaysia PhD scholarship program. M.
Ebert would like to acknowledge the Norman Gordinho PhD
scholarship program at the Electronics and Computer
Science, University of Southampton.
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