ReviewGraphene and its sensor-based applications: A review
Introduction
After the advent of smart sensors around two decades back [1], their applications in daily life have been ever increasing. Nowadays, almost every industrial, domestic and environmental sector utilizes sensors for improving the quality of life [[2], [3], [4], [5], [6], [7]]. Among the sensorial parts, electrodes constitute the most important section as they allow the monitoring unit to receive and analyze the sensed data. Research work has been going on continuously to develop the materials used for electrodes. Existing materials have been improved based on their mechanical, electrical and thermal properties. Gold, silver, aluminum and carbon are some of the commonly used materials used to develop electrodes [[8], [9], [10]]. Out of them, graphene has always been a popular choice due to its distinct advantage of exhibiting excellent electrical and crystal qualities. Graphene, in simple words, can be defined as a single layer of carbon atoms that are tightly packed to form a 2D honeycomb crystal lattice structure [11].
It is the basic component for the carbon allotropes which can be modified into other forms like 0D fullerenes, 1D CNTs, and 3D graphite as shown in Fig. 1. The work on graphene has been going on for the last sixty years, but earlier, it was mostly described as an allotrope of carbon to explain different carbon-based materials. It was just in recent times, around a decade back, the free-standing 2D model of graphene was experimentally proved [12,13]. In the applied field of research, among its wide range of applications, graphene has been mostly used in batteries and cells as anodes, and in supercapacitors due to its low charging time, high strength to weight ratio, and large surface area. It has also found a large number of applications in areas like sensors, biomedical engineering, nano and flexible electronics and catalysis due to its unique properties which include a distinctive nanopore structure, high mechanical strength and high electrical and thermal conductivity. The functionalization of graphene, to reduce the cohesive force between the graphene molecules in different forms, has caused significant changes in its physicochemical properties, thus increasing their end applications [[14], [15], [16], [17], [18], [19], [20]]. Two different forms of functionalization, covalent and non-covalent, are achieved for graphene molecules when the materials are chemically treated by different techniques like spin-coating, filtration, layer-by-layer assembly to cause surface modification but maintaining its intrinsic properties [21]. Even though a lot of research articles have been published based on the different techniques for the preparation of graphene and its utilization in sensors, a thorough research work on the combination of all these aspects is yet to be done. The motivation of this review article is to present a general overview of the importance of graphene as a material, its preparation, and utilization in some of the significant aspects. It showcases the different properties of graphene which makes it a superior element that can be considered for dynamic applications. It also shows a comparative study in the form of tables to highlight the performance of different research studies done on graphene-based electrochemical, strain and electrical sensors. The paper also depicts the strength and limitations of the current sensors along with the challenges and future opportunities of graphene-based sensors.
The involvement of graphene to develop sensors is attributed to some of the distinct advantages like the large surface-to-volume ratio, unique optical properties, excellent carrier mobility and exceptional electrical and thermal properties compared to the other allotropes of carbon. These properties are constant for the double and multi-layered graphene structures. Apart from the difference in the structure, working conditions, the use of these advantages in graphene sensors lie mainly in their capability to adjust according to the application. For example, in strain sensors, properties like the detection limit, maximum sensing range, signal response and reproducibility of the response hold a pivotal role to determine the quality of the sensor. These characteristics are attributed to the electrical and mechanical properties of graphene. In electrochemical sensors, its large surface area helps the loading of the desired biomolecules, resulting in the interaction between the analyte molecule and electrode surface due to the high ballistic transport capability and the very small band gap. Another advantage of graphene lies in its low environmental impact, making it more popular for sensing purposes than other metals [22,23]. Table 1, Table 2 show the comparison of the performance of some of the electrochemical and strain sensors developed with graphene with that of Carbon Nanotubes (CNTs) and silver. It is seen from Table 1 that the Gauge Factors (G.F.) and maximum attainable strain are mostly highest for the graphene-based sensors. One disadvantage of these sensors is the variation in the linearity in their response. For the other two types of sensors, the GFs are much less than graphene sensors, even though most of them attain a fairly high amount of detectable strain. It is seen from Table 2 that, even though the limit of detection achieved by all the three different types of sensors is the same, most of the graphene based sensors are able to achieve high sensitivity with a wider linear range.
Section snippets
Preparation of graphene
Optimization of the preparation of graphene has been performed for some years, since its invention and application. Some of the significant methods that are used worldwide to generate graphene on a large scale are given below.
Properties of graphene
Semi-metallic graphene consists of an arrangement of hexagonal covalently bonded one-atom-thick [86,87] carbon atoms arranged together in a honeycomb lattice structure. Out of four carbon atoms, three carbon atoms exhibit sp2 hybridization. By the hybridization, the trigonal system of carbon atoms exhibits a high bonding energy (5.9 eV), separated with sigma bonds with a bond length of 1.42 Å. The lone p-orbital, being half filled, forms pi bonds with the adjacent carbon atoms [88,89]. The
Electrochemical sensors
Several reasons like a wide range of electrochemical potential, fast electron transfer rate and high redox peaks with linear cathodic and anodic currents have made graphene and its oxidized form (GO) useful as electrochemical sensors for some time.
As mentioned in the earlier sections, with the modifications done on graphene sheets with methods like electrodeposition, polymerization, electrochemical doping, etc., different composite materials were developed for electrochemical sensing purposes.
Strain sensors
Even though strain sensors with different materials have been formulated and developed for a significant amount of time, the graphene-based sensors have proved to be an excellent candidate for strain-sensing applications. The advantage of using graphene over other conductive material for strain sensing lies in the generation of a pseudo-magnetic field due to the shift in the Dirac cones and reduction of the Fermi velocity. The usefulness of this magnetic field lies in its implementation to
Electrical sensors
The use of graphene in electrical and electronic applications has been comparatively minor compared to the preceding explained applications. Graphene has been largely employed as transistors for biomolecular applications. Other uses of graphene-based electrical sensors include temperature sensing, photodetectors, RF applications [[179], [180], [181], [182]], etc. Graphene has been utilized in the form of nanoribbons, nanowires and other forms of nanoparticle arrays. Among the photodetectors,
Challenges with the current sensors
Although there has been a lot of research work done and going on with sensors based on graphene and its different forms, there are still some challenges that need to be addressed at the grass-roots level. The fabrication of graphene is a complex and expensive process. It requires a significant amount of time to generate high-quality graphene. Techniques to generate low-cost graphene are yet to be commercialized. Some of the catalysts used during the growth of graphene increase its toxicity
Conclusion
Some of the significant research work on graphene-based sensors in different fields had been presented in this review paper. The conversion of graphene in different forms increases the dynamicity of its properties, causing an expansion in its applications. There has been some research reported by different groups on complete graphene-based sensing systems [[232], [233], [234]]. Their detection methodologies include mostly electrochemical sensing techniques. The data collected by the sensors are
Future opportunities
Although there have been some drawbacks of graphene and its sensor-based applications as mentioned in the previous section, graphene can still be considered one of the most promising material in the last few decades that have been synthesized in the laboratory and employed for various applications. The number of potential applications using graphene sensors can be increased by converting more of the graphene-based sensors into sensing systems. The sensors can be embedded to form wearable
Mr. Anindya Nag has completed Bachelor of Technology from WEST BENGAL UNIVERSITY OF TECHNOLOGY in 2013 and Master of Engineering at Massey University, Palmerston North, New Zealand in June 2015. His research interests are in the area of Smart Sensors and Sensing Technology for home and environmental monitoring. He is currently pursuing PhD in Engineering at Macquarie University, Sydney, Australia and is working on Printed Flexible Sensors for Human Wellness.
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Mr. Anindya Nag has completed Bachelor of Technology from WEST BENGAL UNIVERSITY OF TECHNOLOGY in 2013 and Master of Engineering at Massey University, Palmerston North, New Zealand in June 2015. His research interests are in the area of Smart Sensors and Sensing Technology for home and environmental monitoring. He is currently pursuing PhD in Engineering at Macquarie University, Sydney, Australia and is working on Printed Flexible Sensors for Human Wellness.
Mr. Arkadeep Mitra received his Bachelor of Technology degree in Electrical Engineering from Kalinga Institute of Industrial Technology, Bhubaneswar, India in 2013 and Master of Science degree in Electrical Engineering from the University of Texas, Arlington in 2017. For his Master of Science research, he worked in simulation IR MEMS sensors. He worked as a software engineer in Aricent, Gurgaon, India, during 2013–2015 testing IEEE protocol for metro Ethernet switches.
Dr. Subhas Chandra Mukhopadhyay (M’97, SM’02, F’11) graduated from the Department of Electrical Engineering, Jadavpur University, Calcutta, India with a Gold medal and received the Master of Electrical Engineering degree from Indian Institute of Science, Bangalore, India. He has Ph.D. (Eng.) degree from Jadavpur University, India and Doctor of Engineering degree from Kanazawa University, Japan. Currently he is working as a Professor of Mechanical/Electronics Engineering with the Department of Engineering, Macquarie University, New South Wales, Australia. He is the Program Leader of the Mechatronics Engineering Degree Program. He has over 26 years of teaching and research experiences. His fields of interest include Smart Sensors and Sensing Technology, Wireless Sensor Networks, Instrumentation and Measurements, Internet of Things, Environmental Measurements, Electromagnetics, Control Engineering, Mechatronics, Magnetic Bearing, Fault Current Limiter, Electrical Machines and numerical field calculation etc. He has authored/co-authored over 400 papers in different international journals, conferences and book chapter. He has edited fifteen conference proceedings. He has also edited seventeen special issues of international journals as lead guest editor and thirty books with Springer-Verlag. He was awarded numerous awards throughout his career and attracted over US$3.0 M on different research projects. He has delivered 296 seminars including keynote, tutorial, invited and special seminars. He is a Fellow of IEEE (USA), a Fellow of IET (UK) and a Fellow of IETE (India). He is a Topical Editor of IEEE Sensors Journal, and an Associate Editor IEEE Transactions on Instrumentation and Measurements. He is in the editorial board of e-Journal on Non-Destructive Testing, Sensors and Transducers, Transactions on Systems, Signals and Devices (TSSD). He is the co-Editor-in-chief of the International Journal on Smart Sensing and Intelligent Systems (www.s2is.org). He was the Technical Program Chair of ICARA 2004, ICARA 2006, ICARA 2009 and IEEE I2MTC 2016. He was the General chair/co-chair of ICST 2005, ICST 2007, IEEE ROSE 2007, IEEE EPSA 2008, ICST 2008, IEEE Sensors 2008, ICST 2010, IEEE Sensors 2010, ICST 2011, ICST 2012, ICST 2013, ICST 2014, ICST 2015 and ICST 2016. He has organized the IEEE Sensors conference 2009 at Christchurch, New Zealand during October 25 to 28, 2009 as the General Chair. He is currently organizing the 11th ICST in Sydney, Australia during December 4–6, 2017, (http://www.cvent.com/d/nvqbb9). He is the Ex-Chair of the IEEE Instrumentation and Measurement Society New Zealand Chapter. He is a Distinguished Lecturer of IEEE Sensors Council from 2017-2019.