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Nanosensors: an overview of sensing

principles in nanotechnology
Paola Vega-Castillo
Instituto Tecnológico de Costa Rica
*Corresponding author:
Instituto Tecnológico de Costa Rica, Cartago, CR30101, pvega@itcr.ac.cr

Abstract fast response, high sensitivity and selectivity, low power


consumption, size compatibility with biological species, and
Nanosensors are expected to offer a solution for recovery at room temperature or under heating. Nanosensors
ultrasensitive sensing at low cost, small size and low power can be based on nanostructured materials such as porous
consumption for physical, chemical and biological silicon, nanoparticles, nanosondes, nanowires and
variables. This paper presents a brief overview of sensing nanoelectromechanical systems (NEMS), the latter
principles in nanotechnology, the advantages and challenges commonly based on mechanical deformation or
in implementing nanosensors. microfluidics. Among their possible configurations, the
most popular is the nanowire field effect transistor.
However, other configurations also make possible the
Keywords: sensors, nanotechnology, nanosensors, implementation of effective nanosensors, such as capacitors.
sensing principles.
2. FET nanosensors
1. Introduction
In conventional FET sensors, the dielectric is directly
The high integration density of nanosensors and the ability exposed to the analyte instead of fabricating a gate
for molecular detection makes them an attractive option for electrode. When enough analyte molecules deposit on the
medical, chemical and biological sensing. Chemical dielectric, their charge can either increase or decrease the
nanosensors may find applications related to security, transistor current depending on whether the analyte causes
environmental and agricultural sensing and food industry. depletion or inversion at the dielectric-substrate interface. In
Sensors can be functionalized to detect a either a specific this approach, the minimum exposed surface required for
analyte or a group of substances with the same functional sensing may be an issue for scaling down.
group and therefore with similar characteristics.
On the other hand, a typical nanosensor relies on a nanowire
Due to their small size, an array of sensors can be built in a or nanotube-based field effect transistor, for which
small area. By combining sensors with different semiconducting nanowires are made of carbon nanotubes,
functionalization in the same array, complex analytes can be silicon or other materials.
detected, for example, emulating an electronic nose.
Moreover, advances in nanotechnology may lead to new Figure 1 shows a schematic cross section of a nanosensor
sensing principles. based on nanowires. The nanowire is deposited on a
semiconductive or degenerate [1] substrate, with a thin
In addition to the advantage of size, nanosensors have the insulating layer between them. This insulating layer is
potential to overcome traditional sensors in the following typically fabricated by dry thermal oxidation of the
aspects: substrate. The nanowire is contacted on both extremes. The
degenerate substrate operates as a backgate for the CNT
• Sensibility: an increased output amplitude in response
channel. When the substrate is semiconductive, the analytes
to the same input magnitude
act as gate. Alternatively, the gate can be replaced by a
• Resolution: a smaller change in the input magnitude liquid [1].
required to generate a detectable change in the output
Analyte
• Selectivity: increased ability to distinguish a specific Linking
agent among a group of agents molecule
Current
• Response time: decrease the sensor´s time constant τ
Contact
• Reversibility: increased ability and speed to return to its
original conditions alter a sensing cycle. Insulator
Substrate
Nanosensors offer advantages such as high integration
density, large surface area to volume ratio, high aspect ratio, Figure 1. General scheme of a nanowire sensor.
Once the basic nanowire FET structure has been fabricated, distribution can be changed to meet a specific sensing
selectivity for sensing specific biological or chemical requirement.
species can be achieved by means of sensor
functionalization, that is, the addition of molecular receptors The most common molecular sensor based on MEMS is a
to the nanowire. cantilever whose displacement is caused by interaction with
the analyte, for example, by means of hydrogen bonds, van
Sensing of biological species can be achieved by combining der Waals forces or electrostatic interactions, which modify
a biological recognition component (bioreceptor) with a the surface stress, the cantilever mass or both. The surface of
physical-chemical detector. The bioreceptor can be a living the cantilever is functionalized to detect specific chemical or
biological system such as a cell, tissue or organism, or a biological species. Both static deformation and resonant
molecular biological species such as antibodies, proteins or operation can be used as transduction signals. As in case of
enzymes. Recognition of proteins, viruses, chemicals, AFM tips, cantilever bending is measured by laser
antibodies, enzymes, vitamins and molecular detection of deflection.
diseases are some of the envisioned applications for these
biosensors. The use of nanoporous thin layers in cantilevers was found
to increase their deformation due to higher surface stress [7].
Nanowires are an excellent option for sensor scaling due to The thickness of the nanoporous material and the density,
the large mobilities causing carrier flow at ballistic size and geometry of the pores have been identified as
velocities. In nanowire-based sensors, the high ratio of adjustable parameters to reach a specific cantilever bending
surface to volume atoms increases the reactivity of the or resonant frequency [7].
nanowire since most of the atoms of the nanowire are
exposed to the analyte and due to their small amount, the Capacitive sensors reported in literature have been used in
effect of a single molecule on the nanowire resistance is detection of chemicals in the gas phase by adsorption of the
much noticeable than in substrate channels of conventional chemical of interest on the functionalized capacitor [9]. A
FET sensors. This allows the implementation of highly fast adsorption rate leads to a fast sensor response.
sensitive devices capable of sensing a single molecule with
fast response. Metal-insulator-semiconductor (MIS) capacitors have also
been used together with nanoporous materials to create
In addition to that, these sensors present high sensitivity to nanosensors. In this case, nanoporous materials are
adsorbates. Moreover, they also ease electron transfer in deposited to one electrode of the capacitor to change its
chemical reactions with proteins and increase molecular charge and potential by chemical reaction with the analyte
adsorption. or its adsorption.

The change in the I-V characteristics of the transistor can be The dielectric can also be coated with carbon nanotubes to
caused by: form an electrode; the CNTs are contacted with metal
electrodes. A degenerate substrate serves as the second
1) carrier transfer from the analyte to the nanotubes, acting electrode. The degenerated substrate is oxidized to create a
as nanowire doping [2, 3] and therefore increasing or 250nm SiO2; CNTs are deposited by chemical vapor
decreasing the current due to modification of the threshold deposition and contacted by Pt electrodes [9]. A general
voltage. The surface potential of the nanotube is modified by schematic draw of this sensor is illustrated in figure 2. Here,
the analyte, causing causing accumulation or depletion [4, 5] adsorbate polarization is achieved by the fringing electric
fields at the CNT surface. This additional polarization
2) change in the capacitance of the nanowire [1] by increases the capacitance. These sensors are capable of
attraction or repulsion of charge by the analyte, causing a detecting even a monomolecular layer.
similar effect as a change in permittivity
Contacts to CNTs
3) modification of the energy levels at the contact due to
adsorption of the analyte at the nanowire contacts [2]

4) change in mobility due to the scattering caused by the Pt


adsorbed analyte at the surface of the nanotubes [3]; a SiO2
similar effect may be caused by analytes enclosed by the Degenerate Si
nanotube
CNTs

3. MEMS/NEMS sensors

The sensibility of MEMS/NEMS sensors can be enhanced


by the large surface area of nanoporous materials, which
increase adsorption and chemical reactivity of sensors, and Bottom electrode
have been used to modify electrodes for potentiometric
sensing [6], cantilever sensors [7], conductometric sensing
[8]. The advantages of nanoporous materials for sensor Figure 2. Schematic of a capacitive chemical sensor [9]
applications are related to the increase on surface area and
the possibility to modify and functionalize a surface. On the other hand, nanowire forests made of carbon
Besides funcionalization, pore length, size, geometry and nanotubes can be grown to provide electrical connection
between the analyte and a metal electrode.
Also, a humidity sensor was built based on a nanoporous
membrane contacted by electrodes. Three materials were
tested: polyester, polycarbonate and cellulose acetate [8]. 4. Challenges [15]
Humidity was measured as a change of capacitance,
resistance, or both due to enhanced water adsorption caused The trends in miniaturization are now beyond Moore´s law
by the nanopores. Although the most common approach for and a “More than Moore” approach is required to provide
sensing is based on adsorption, absorption-based sensors electronic systems increasing functionality and therefore
have also been demonstrated. Both effects have been applied added value. Nanosensors can be the answer to this need.
to change the permittivity or the conductivity of the sensing However, one of the issues to be solved in order to
layer. A schematic of the sensor is presented in figure 3. implement nanosensor products is the development of
methods for mass production and compatibility with silicon
technology for on chip integration and connection in
Contact System-on-Package products and packaging. The fabrication
Nanoporous membrane
cost must of nanosensors must decrease, reliability and
Gold
reproducibility must reach the level of maturity of silicon
technology.

Sensing with CNTs implies control of their chemical


properties (including their chirality), their physical
properties (nanotube dimensions), their functionalization
and the fabrication of good electrical contacts. Electronic
devices such as CNT FETs require semiconducting single
wall CNTs (SWCNTs). In most synthesis methods, the
resulting material contains both metallic and semiconducting
nanotubes or the resulting CNTs are multiwalled. High
Contact control of the CNT synthesis for low spread of the nanotube
diameter is quite important, since metallic or
semiconducting behavior is determined by this variable.
Figure 3. Schematic of a sensor based on nanoporous Moreover, for semiconducting nanotubes the band gap is
membrane [8] determined by the nanotube´s diameter. Furthermore,
advances in research are required to achieve batch
A change in mechanical or electrical resonance frequency fabrication of horizontally aligned semiconducting
has been used in gas sensors. As an example, a resonator SWCNTs for mass production.
coated with carbon nanotubes experiences changes in the
resonance frequency in response caused by modification of In case of other nanowires, both nanowire diameter and
the permittivity of CNTs under exposure to NH3 [10]. In doping are key properties to control.
surface acoustic wave sensors, adsorption on a substrate
between the input and output wave transducer leads to a When implementing biosensors, size compatibility is an
change in conductivity [11] or mass [12] which shifts the important aspect to consider. The sensor must interact with
resonant frequency. molecules, typically DNA and proteins. Besides high
selectivity, sensibility and resolution must be high enough to
Ionization gas sensors based on carbon nanotubes have been enable detection using the lowest possible amount of cells or
reported in literature [13]. A schematic of this sensor is tissue.
presented in figure 4. The working principle of these
sensors is the gas ionization under high electric fields, which Two of the biggest challenges of nanobiosensors real time
cause an emission current peak to flow at a breakdown sensing and monitoring cells in vivo. This implies not
voltage that is characteristic of the gas. Due to the ability to having to purify or isolate the agent, which is carried out
grow dense “forests” of vertically aligned CNTs and their prior to sensing with traditional sensors. Real time
high aspect ratio, the nanotubes are used as ionization tips monitoring would provide detailed information that may
that create high electric fields at lower voltages than greatly increase the understanding of biological processes,
traditional ionization sensors, with reported voltages as low identification of the specific agents involved and the
as 20V [14]. Since their operation is not based on a duration of the processes.
chemical reaction, these sensors are faster.
On the other hand, a highly desirable application for
nanosensors is the molecular disease diagnose. However,
this is a complex task, since diagnose involves
Al Cathode determination of the amount and activation level of the
agent, and must also relate the agent with the state of the
Insulator
disease.
Si Anode
CNTs 5. Conclusions

The main methods of sensing in nanotechnology were


presented, together with typical examples of these sensors
and their applications. Nanosensors have great potential to
Figure 4. Gas ionization CNT sensor [13]
make the semiconductor industry achieve the “More than
Moore” breakthrough. The challenges to overcome for mass
products were presented.

6. References

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[10] Chopra, S. et al. Selective gas detection using a


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[11] Sivaramakrishnan, S. et al. Carbon nanotube-coated


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