A Review on Graphene based Field Effect Transistor

Rizwanur Rahman, Department of Chemical Engineering, University of Utah

The detection of different biomarkers e.g., protein is important for the diagnosis and
monitoring of diseases. However, the cost and time delays of traditional protein detection
techniques are obstacles to the widespread use of biomarker measurements in medicine. Many
new alternatives to traditional protein assays are being actively pursued. Among these
nanoscale field-effect transistor (nanoFET) biosensors are showing imminent promise which are
typically made from either semiconducting carbon nanotubes (CNTs), silicon nanowires, or
graphene.

FET-based biosensors can offer advantages as compared to other electrochemical sensors in

terms of higher sensitivity, selectivity with fast response time, and nanoscale fabrication
procedures and device dimensions. A change in conductivity upon interaction of biomolecules
with the nanostructure's surface is the typical sensing mechanism for the FET biosensors.
NanoFET devices are sensitive to the electrostatic charge of target biomolecules. The electrical
resistance of the nanomaterial changes when charged molecules bind near the material
surface. Graphene, an atomically thin sheet of carbon atoms, is particularly promising as the
electric-field-sensitive component of nanoFET biosensors. The two-dimensional nature of
graphene leads to the additional advantage that all atoms in the transistor channel are
electrostatically coupled to the environment. Graphene has high sensitivity to electrical
perturbations due to its ultra-small thickness and high carrier mobility at room temperature.
Graphene sheets blanket surfaces, which allows the sensing area to be maximized for a given
amount of on-chip real estate. Although graphene-based biosensors present excellent
performance in biomolecular detection, the sensor performance should be further improved to
meet demanding requirements in terms of sensitivity, selectivity and stability; the sensor
fabrication method also should be suitable for large-scale manufacturing critical for future
product and technology commercialization. The objective of this review paper is to discuss
different types of graphene-based field effect transistors and their applications to detect
biomarkers in different environments. The pros and cons of different biosensors will also be
discussed. Finally, we will also discuss the prospects of graphene-based biosensors.

Ohno et al. [1] investigated electrical detection of pH and protein (bovine serum albumin, BSA)
by an electrolyte-gated graphene. The transfer characteristics and conductance of the FET were
evaluated at pH levels varying from 4.0 to 8.2. Label-free detection of BSA protein was
performed using phosphate buffer solution containing BSA, and the conductance changes of
the device were measured on adsorption of BSA on graphene at various gate voltages. The
conductance changes increased linearly at low concentrations and saturated at higher
concentrations. Protein could be detected at concentrations as low as 0.3 nM. Similarly, Huang
et al. [2] detected glucose and glutamate molecules by conductance changes of a graphene
transistor fabricated from CVD-grown graphene film. Transfer characteristics of the FET were
measured in a top-gate configuration using an Ag/AgCl electrode in PBS solution. The device
was functionalized with glucose oxidase (GOD) or glutamic dehydrogenase (GluD) depending on
the requirement for glucose or glutamate detection. Fig.1 shows a schematic diagram of a FET
based biosensor functionalized with GOD.

Figure 1: Schematic diagram of glucose oxidase functionalized graphene FET.

One of the major factors which significantly affect the performance of graphene-based FET
sensors is the trapped charge at the interface and in the silicon dioxide. These trapped charges
degrade transport properties of the FET device and their performance as a biosensor. To avoid
the effect of trapped charges suspended graphene devices have been fabricated. Cheng et al.
[3] demonstrated that the suspension of the graphene sensing element above the substrate
enhanced its electrical properties with increased signal-to-noise ratio for use as a real-time and
sensitive pH sensor. By suspending the graphene, the Dirac point shifted from 0.1 V to 0 V, and
the transconductance of the device increased 1.5–2 times for hole and electron carriers. By
applying solutions with different pH values ranging from 6 to 9, the Dirac point of the
suspended graphene FET shifted positively and exhibited similar properties in both p-type and
n-type transistor modes. The transconductance improved by a factor of 2 and the signal-to-
noise ratio of the suspended graphene device increased by 14 dB for both the hole and the
electron carrier. Hence, the enhanced performance of suspended graphene devices is
successful in low detection limit in a solution for chemical and biological sensing in comparison
to their counterparts supported on substrates. Mohanty et al. [4] demonstrated interfacing of
chemically modified graphene with biological systems in a live-bacteria-hybrid device and a
DNA-hybridization device with excellent sensitivity. The electrical measurements revealed that
the chemically modified graphene sheets were p-type semiconductors with high resistance and
low carrier mobility. Electrical measurements revealed that the selective tethering of the single-
stranded DNA (ssDNA) on GO led to a 128% increase in conductivity which was attributed to the
attachment of the negatively charged DNA on the p-type GO. Subsequent hybridization with
cDNA led to further increase in conductivity and was completely reversible during cycles of
denaturing and rehybridization. Also, the negatively charged bacteria and protein could be
electrostatically adsorbed on positively charged graphene amine and survived for up to 4 h
duration. This extremely high sensitivity of graphene amine was attributed to the extensive
aminization of GO to form graphene amine, where ethylenediamene bonding on GO partially
acts as gating process for the graphene sheets.

Shun Mao et. al. [5] fabricated a graphene-based FET through direct growth of Vertical
Graphene (VG) sheets in lieu of traditional horizontal graphene sheets on the sensor electrode
(Fig.2). The FET sensor is constructed as the sensing channel, whose conductivity change is
measured as the sensing signal through transistor and direct-current measurements. This
sensor configuration allows for the direct diffusion and binding of the target protein (antigen in
the solution) to the probe protein (antibody functionalized on the Au NP).

Figure 2: Direct growth of vertically oriented graphene for FET.

The resistance measurement results indicated that the VG conductivity level was like that of
graphene. The binding between the VG and gold electrode was found strong because VG was
directly grown on the gold electrode under a high temperature (700°C) and the gold electrode
surface was partially melted and merged with the VG during the VG growth process. Therefore,
the contact resistance between the VG and the electrode was found small. Since the VG was a
vertical structure, there were very few Au NPs around the VG-electrode contact area.
Therefore, there were limited proteins attached in the contact area during the sensing and the
change in the sensor conductance was mainly from the VG channel. Transistor measurements
from the sensor showed that the VG is a p-type semiconductor with a low Id under a positive
gate potential. Similarly, Kehan Yu et. al. [6] grew vertically oriented graphene sheets through
strategically patterning gold electrodes on the SiO 2 surface. CNWs were successfully grown on
grounded, microfabricated straight gold stripes and gold UWM logos. Both experimental and
modeling results suggested that the electric field distribution above the substrate material plays
a key role on the CNW coverage. Additionally, the electric field distribution was strongly
affected by the field screening effect. A reliable gas sensing FET fabrication was demonstrated
with the electric-field induced patterning growth. The CNWs exhibit p-type semiconducting
properties in ambient conditions and sensitivity to low-concentration NO 2 and NH3.

Recently, Yasuhide et. al. [7] investigated label-free immunosensor based on aptamer modified
graphene field effect transistor. They immobilized Immunoglobulin E (IgE) aptamers with an
approximate height of 3 nm on a graphene surface and confirmed by atomic force microscopy.
The aptamer-modified G-FET showed selective electrical detection of IgE protein whereas other
proteins were not detected; these findings indicate that nonspecific binding of nontarget
proteins was successfully suppressed. From the dependence of the drain current variation on
the IgE concentration, the dissociation constant was estimated to be 47 nM, indicating good
affinity and the potential for G-FETs to be used in biological sensors. Aptamer-based
immunosensors have been intensively investigated in recent years. Liss et al. [8] developed
aptamer-based quartz crystal microbalance biosensors with KD values of several nanomolar.
Mendonsa and Bowser [9] reported aptamer−IgE reactions using capillary electrophoresis, and
their average KD was 29 nM.

Graphene based detectors can also be used to detect DNA. GFET DNA sensors are unique
among other nucleic acid detection methods due to their label free detection. This allows for
direct detection of oliogonucleotides within a sample without any prior alteration of the
sample. These devices can be separated into two different assembly schemes: back-gated and
liquid-gated. Back gated GFETs are less frequently employed as DNA sensors due to the
difficulties associated with producing devices requiring small gate voltages (VG) rather than the
more commonly and readily prepared higher gate voltage devices [4]. However, Kybert et al.
[10] reported the use of DNA-decorated graphene for arrays of chemical vapor sensors which
demonstrated a significant shift in the VG required to observe the minimum in the device
conductance (VG, min) after DNA deposition. ssDNA was adsorbed onto the surface of graphene,
which allowed for chemical vapor sensing down to parts-per-billion as analyte binding further
shifted the VG, min. Liquid-gated graphene field effect transistors have recently been shown to
detect DNA with sensitivities down to 0.01 nM and capabilities of detecting single mismatches
[11]. The distinction between back- and liquid-gated GFETs is the potential for current to flow
between the graphene and the gate electrode via the aqueous ionic solution separating the two
conductive bodies. However, gate current leakage is limited, at low gate bias, by the formation
of an ionic double layer (Debye layer) formed along the surface of the graphene and gate
electrode due to the voltage bias. At higher gate bias potentials, the onset of electrolytic
processes leads to high gate currents.

Given the many promising early results from graphene-based FETs, it can be concluded that
their future is very bright. Not only is graphene superior to carbon nanotubes in most types of
electrochemical sensing, but it also may prove to be a less expensive option making it an
attractive alternative for large-scale manufacturing. However, controlled methods of graphene
synthesis, particularly via in-line as opposed to batch processes, with enough process control of
layer number and footprint area remain to be developed. The interaction of DNA and graphene
also allows for efficient binding of oligonucleotides to the sensor surface but has been shown to
disrupt the hydrogen bonding forces between complementary strands. This is potentially
problematic for the use of DNA nanostructure sensors as spatial resolution may be lost.
Stabilizing the interaction between DNA nanostructures and graphene is an important problem
to address and is an active area of research in our group. From a fundamental perspective,
some of graphene's intrinsic characteristics as well as biosensing capabilities requires further
study. The effects of oxygen moieties on the electrochemical characteristics of the substrate
still require clarification, as existing results are somewhat inconsistent. Another area that
deserves expanded attention is the biocompatibility of graphene in different sensing
applications; even though initial studies have yielded positive reports of graphene's ability to
support cell proliferation more biological systems and related ambient conditions need to be
addressed.
References

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