QCM Coating With rGO Material as a Platform

Developing Piezoelectric Biosensor

Dody Susilo Totok Mujiono Darminto
Departement of Electrical Engineering Departement of Electrical Engineering Departement of Physics
Institut Teknologi Sepuluh Nopember Institut Teknologi Sepuluh Nopember Institut Teknologi Sepuluh Nopember
Surabaya, Indonesia Surabaya, Indonesia Surabaya, Indonesia
susilodody.17071@mhs.its.ac.id totok_m@ee.its.ac.id darminto@physics.its.ac.id

Abstract—Quartz Crystal Microbalance (QCM) is one of the

piezoelectric material common for sensor application in either II. MATERIAL AND METHOD
gas or liquid phase. By immobilizing a thin layer of bio-element
on QCM surfaces, it is possible to develop a biosensor suitable A. Graphene Oxide
for many applications. Interaction between bio-element and its Graphene is a nanocarbon material that has unique
associate materials of the material deposit into the QCM
properties such as having a specific surface area (2630m2g-1),
surfaces and change the QCM frequency. To improve the quality
of the biosensor, a biocompatible material such as Reduced high intrinsic mobility (200,000cm2v-1s-1), high young
Graphene Oxide (rGO) need to be deposit first. This paper modulus (~1.0Tpa) and thermal conductivity (~5000Wm-1K-
1
develops a simple technique that immobilize rGO material on ), and its optical transmittance (~97.7%) and good electrical
the surface of QCM. An rGO solution was prepared and then conductivity need attention for applications such as for
sprayed to the QCM surfaces. After drying process, frequency transparent conductive electrodes, among many other
characteristics of the QCM was measured. For the measurement potential applications [6].
process, 24-bit FPGA-based frequency-counter with 1 Hz GO is layered and oxygenated graphene sheet that contain
resolution has been designed. Measurement results shows that oxygen functional group (such as carboxyl and epoxides) on
proposed coating method suitable for biological element
its edge and surface. The presence of oxygen functional group
immobilization.
may enhance the charge transfer, solubility and
Keywords—Biosensor, FPGA, Frequency Counter, rGO, biocompatibility. GO transform into rGO with some residual
QCM oxygen and structural defect. The graphene family can used
as a sensor or support for another biosensor materials, such
I. INTRODUCTION as enzyme or protein.
The rGO may improve the analytical response of sensor
Biosensor has been grown rapidly in the last ten years or biosensor mainly their sensitivity. In this research rGO was
because of its advantages for sensing, especially in its provided by Material Laboratory, Physics Department, ITS
selectivity and sensitivity [1]. Biosensor is an analytical tool Surabaya [7].
consist of biological element and transducer that convert a
biological signal into an electrical signal [2]. The biological B. Quartz Crystal Microbalance
element, which responsible to biosensor interaction with QCM is a quartz crystal resonator that the resonant
analyte, includes enzyme, antibodies, cell, etc. Transducer frequency affected by the rGO was provided by physic was
will translate the biological or chemical change during the deposited on the electrode surface. The working principle of
biological element interaction with analyte to an electrical or QCM is based on the piezoelectric effect. QCM is shown in
optical signal. Figure 1.
Including to the transducer are amperometry, mechanical,
piez oelectric, optical, etc. Biosensor found many
applications in many areas such as agriculture, health,
environment, and industrial [3]. QCM is one of the
piezoelectric material common for sensor application in
either gas or liquid phase [4]. By immobilizing a thin layer of
bio-element on QCM surfaces, it is possible to develop a
biosensor. Interaction between enzyme (bio-element) and its
associate molecules makes some molecule deposit into the
QCM surfaces.
This material deposit will change the QCM frequency. By
connecting the QCM to the oscillator circuit, it is possible to
detect the frequency change between before the bio-element
interaction and after. This paper deal with a development of
simple technique immobilize a thin layer of rGO material on Fig 1. Quartz Crystal Microbalance
the surface of QCM. Reduced graphene oxide is a new
material and found useful applications in many areas [5].
Because of rGO characteristics, it can be used as a based layer
for biological element to improve biosensor quality.
 The resonant frequency changes as a function of
deposited were formulated by Sauerbrey in the equation:
2𝑓 2
𝛥𝑓 = − (𝜌𝑣𝐴) 𝛥𝑚 (1)
where:
𝛥𝑓 is observed frequency changes (Hz).
𝑓 is the basic resonance frequency (Hz).
𝛥𝑚 is a change in mass per unit area (kg).
𝜌 is crystal density (kg/m3).
𝑣 is the speed of acoustic propagation in crystals (m/s).
𝐴 is the area of the electrode (m2).
The piezoelectric crystal detector can be a very powerfull
analytical tools because of the reletionship show for the
change in frequency so the analytic concenteration with high
sensitivity. The crystal detector change the frequency due to
the deposition of was on its surface. To attarct spesific
Fig 3. Oscillator Circuit
material, a thin film anociated with it can be deposit on QCM
surface. A QCM with gold electrode was used in the D. Preparing Reduce Graphene Oxide Solution
experiment[8]. The process of making rGO is several stages, namely the
C. Electronic Circuit main ingredient in making rGO is coconut shell. Coconut
shells are cleared by sticking fibers and dried for ± 2 hours
The block diagram of the electronics system shown in
using the hot sun. After drying, the coconut shell is burned.
figure 2. A QCM, with specific thin layer on its surfaces, is
This burning is done until the shell becomes charcoal (± 30
connected to the oscillator circuit which drive QCM to
minutes), this material is called GO. After becoming GO,
resonate at its characteristic frequency. The resonant
then leave it to cool and pound. Then the GO is put into the
frequency calculates by frequency counter. The obtained
Crucible and the furnace process is carried out at a
frequency then displayed and send to the computer PC. The
temperature of 400°C for 5 hours so that it becomes a rGO.
schematic diagram of the QCM and its oscillator circuit
rGO material was crushed using Mortar and Pestle, then
shown in Figure 3. Beside the QCM, it is consisting of two
filtering using Mesh was carried out by 200. The rGO
oscillator, one resistor and two inverters.
material is ready to be used for the next process. The process
of making rGO solution with DMSO there are several stages,
namely the material prepared is rGO and DMSO. Comparison
of the solution is 1 Gram rGO and 10 mL DMSO, then the
solution is put into a Baker glass. The next process is mixing
the solution using Ultrasonication for 2 hours. The process of
making rGO solution with DMSO is shown in Figure 4.

Fig 4. Process of Making rGO Solution

Fig 2. Overall System Block Diagram
The frequency counter and display were implemented on
DE-10 Lite FPGA board. The main reason of using FPGA
board is because it is possible to develop a flexible size if
counter. In this research, a 25bit frequency counter is used for
9 MHz oscillator circuit. This counter can be used for 16 MHz
with single Hz resolution. The counting result will be both
displayed on 6 available 7-segment displays and send to PC
for further processing.
E. Sensor Development Process
The process of developing the sensor can be done in
several stages, namely coating QCM with Graphene, which
uses several stages, namely cleaning the surface of QCM with
Ethanol. After further cleaning, coating with Graphene uses
the Spray Technique. The QCM coating process has several
cleaning the QCM surface with Ethanol. Step first, this step is
used to clean the surface of the QCM from oil and small
particles. Then the QCM soaked with Piranha Solution for 5
minutes.
This step is used to make the QCM surface Hidropilic.
Coating QCM with rGO solution was performed by spraying
for several second. In this experiment, QCM was sprayed in 3 B. Frequency Shift Of The Coated QCM
times duration, 5 second (type A), 15 second (type B), and 25 The QCM coating process uses 1 gram rGO solution with
second (type C). It is assigned several hundreds Hz normally 10 mL DMSO with the Spray technique. In testing the
needed the longer time duration resulted in the thicker rGO
frequency difference (∆F) QCM uses a layer of rGO and
layer. After that, the QCM driyed in the oven with temperature
DMSO with spray techniques for type A, type B, and type C
40-60°C for 3-5 minutes.
there is a change in frequency, the longer the coating process
the greater the difference in frequency (∆F).
Table 1. Difference Test Results Frequency (∆F) QCM With
Solution rGO and DMSO for 5, 15 and 25 seconds
Frequency ∆F (Hz)
Experiment
Type A Type B Type C
1 -35.5 -114 -269
2 -34.5 -170 -215
3 -46 -124 -249
4 -46 -134 -239.5
5 -32 -104.5 -189
6 -32.5 -168.5 -204.5
7 -23 -120 -190
Fig 5. QCM Coating Process 8 -15.5 -128 -172.5
9 -13.5 -146.5 -194.5
III. RESULT AND DISCUSSION 10 -16 -123 -204

A. rGO Characterization
Figure 7 shows that the spray technique for 5 seconds, the
The rGO characterization is intended to check the size highest value of the upper limit is 46 Hz, the lowest value of
distribution of the rGO on the solution. The characterization the lower limit is 13.5 Hz and the Q2 value is 32 Hz. While
was performed using Particle Size Analyzer (PSA) (Zetasizer 15 seconds, the highest value of the upper limit is 170 Hz, the
Nano Series). Figure 5(a) and 5(b) show the size distribution lowest value of the lower limit is 104.5 Hz and the value of
by intensity and size distribution by volume respectively. Q2 is 128 Hz. and 25 seconds, the highest value of the upper
The intensity characterization test using PSA is a particle size limit is 269 Hz, the lowest value of the lower limit is 172.5
of 570.6 d.nm and a standard deviation of 326.5 d.nm while Hz and the value of Q2 is 204 Hz.
the volume characterization is a particle size of 655.4 d.nm Table 2. Analysis of Quartiles from Experiments
and a standard deviation of 380.7 d.nm. This size is small for Time of spraying
our purpuse. In this study the size of the material used 5 Seconds 15 Seconds 25 Seconds
especially this rGO has a nanoscale size. Characterization Upper 46 Hz 170 Hz 269 Hz
Q3 35.5 Hz 146.5 Hz 239.5 Hz
testing of rGO solution with DMSO using a PSA is shown in
Q2 32 Hz 128 Hz 204 Hz
Figure 6. The standard deviation of particle size is the value Q1 16 Hz 120 Hz 190 Hz
used to determine the distribution of data in the sample, and Lower 13.5 Hz 104.5 Hz 172.5 Hz
determine the individual data points or the average value of
the sample.

(a)

Fig 7. QCM Frequency Changes With Quartile Analysis

IV. CONCLUSION & FUTURE WORK
In this paper, coating a QCM with rGO material as a
platform for biosensor development is presented. The
(b) intensity characterization test using PSA is a particle size of
Fig 6. Characterization Test (a) Intensity (b) rGO Solution 570.6 d.nm and a standard deviation of 326.5 d.nm while the
Volume 1 Gram with DMSO 1 mL volume characterization is a particle size of 655.4 d.nm and a
standard deviation of 380.7 d.nm. It is consist of preparing
the rGO solution, spraying it coating the QCM by for some
duration of time, and characterizing it QCM characterization
result show that type B and type C can be used as a base
(platform) for biosensor development. Next in our research in
immobolizing above the rGO layer. Measurement results
shows that proposed coating method suitable for biological
element immobilization.
ACKNOWLEDGMENT
We thanks to Prof Takamichi Nakamoto for providing the
QCM and the support of financial assistance from Takamichi
Nakamoto of Tokyo Institute of Technology.
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