Metal-Organic Frameworks Meet Molecularly Imprinted Polymers: Insights and Prospects for Sensor Applications.

The use of porous materials as the core for synthesizing molecularly imprinted polymers (MIPs) adds significant value to the resulting sensing system. This review covers in detail the current progress and achievements regarding the synergistic combination of MIPs and porous materials, namely metal/covalent-organic frameworks (MOFs/COFs), including the application of such frameworks in the development of upgraded sensor platforms. The different processes involved in the synthesis of MOF/COF-MIPs are outlined, along with their intrinsic properties. Special attention is paid to debriefing the impact of the morphological changes that occur through the synergistic combination compared to those that occur due to the individual entities. Thereafter, the strategies used for building the sensors, as well as the transduction modes, are overviewed and discussed. This is followed by a full description of research advances for various types of MOF/COF-MIP-based (bio)sensors and their applications in the fields of environmental monitoring, food safety, and pharmaceutical analysis. Finally, the challenges/drawbacks, as well as the prospects of this research field, are discussed in detail.

Metal-organic frameworks for advanced transducer based gas sensors: review and perspectives.

The development of gas sensing devices to detect environmentally toxic, hazardous, and volatile organic compounds (VOCs) has witnessed a surge of immense interest over the past few decades, motivated mainly by the significant progress in technological advancements in the gas sensing field. A great deal of research has been dedicated to developing robust, cost-effective, and miniaturized gas sensing platforms with high efficiency. Compared to conventional metal-oxide based gas sensing materials, metal-organic frameworks (MOFs) have garnered tremendous attention in a variety of fields, including the gas sensing field, due to their fascinating features such as high adsorption sites for gas molecules, high porosity, tunable morphologies, structural diversities, and ability of room temperature (RT) sensing. This review summarizes the current advancement in various pristine MOF materials and their composites for different electrical transducer-based gas sensing applications. The review begins with a discussion on the overview of gas sensors, the significance of MOFs, and their scope in the gas sensing field. Next, gas sensing applications are divided into four categories based on different advanced transducers: chemiresistive, capacitive, quartz crystal microbalance (QCM), and organic field-effect transistor (OFET) based gas sensors. Their fundamental concepts, gas sensing ability towards various gases, sensing mechanisms, and their advantages and disadvantages are discussed. Finally, this review is concluded with a summary, existing challenges, and future perspectives.

Highly Selective Self-Powered Organic-Inorganic Hybrid Heterojunction of a Halide Perovskite and InGaZnO NO2 Sensor.

Self-powered sensors can lead to disruptive advances in self-sustainable sensing systems that are imperative for evolving human lifestyles. For the first time, we demonstrate the fabrication of a heterojunction sensor using p-type hybrid-halide perovskites (CH3NH3PbBr3) and an n-type semiconducting metal oxide thin film [InGaZnO (IGZO)] for the detection of NO2 gas and power generation. Combining the excellent photoelectric properties of perovskites and the remarkable gas-sensing properties of IGZO at room temperature, the devised sensors generate open-circuit voltage and modulate according to the ambient NO2 concentration. The major challenge in devising self-powered gas sensors is to attain harvesting capability and selectivity simultaneously, owing to perovskites reactivity in the presence of oxygen and humidity. In this work, we developed a novel approach and fabricated a heterojunction sensor using parylene-c as an additional layer to curb the cross-sensitivity and to enhance the selectivity of the sensor. Even under the low concentrations of NO2, the developed sensor exhibits remarkable sensitivity, selectivity, and repeatability. The devices are sensitive and robust even under extreme humidity conditions (80% RH) and synthetic air. The devised sensor configuration is one way to eliminate the cross-sensitivity issue of the perovskite-based devices and serves as a reference for the development of self-powered sensors.

Gas sensing materials roadmap.

Gas sensor technology is widely utilized in various areas ranging from home security, environment and air pollution, to industrial production. It also hold great promise in non-invasive exhaled breath detection and an essential device in future internet of things. The past decade has witnessed giant advance in both fundamental research and industrial development of gas sensors, yet current efforts are being explored to achieve better selectivity, higher sensitivity and lower power consumption. The sensing layer in gas sensors have attracted dominant attention in the past research. In addition to the conventional metal oxide semiconductors, emerging nanocomposites and graphene-like two-dimensional materials also have drawn considerable research interest. This inspires us to organize this comprehensive 2020 gas sensing materials roadmap to discuss the current status, state-of-the-art progress, and present and future challenges in various materials that is potentially useful for gas sensors.

Selective Toluene Detection with Mo2CTx MXene at Room Temperature.

MXenes are a promising class of two-dimensional materials with several potential applications, including energy storage, catalysis, electromagnetic interference shielding, transparent electronics, and sensors. Here, we report a novel Mo2CTx MXene sensor for the successful detection of volatile organic compounds (VOCs). The proposed sensor is a chemiresistive device fabricated on a Si/SiO2 substrate using photolithography. The impact of various MXene process conditions on the performance of the sensor is evaluated. The VOCs, such as toluene, benzene, ethanol, methanol, and acetone, are studied at room temperature with varying concentrations. Under optimized conditions, the sensor demonstrates a detection limit of 220 ppb and a sensitivity of 0.0366 Ω/ppm at a toluene concentration of 140 ppm. It exhibits an excellent selectivity toward toluene against the other VOCs. Ab initio simulations demonstrate selectivity toward toluene in line with the experimental results.

Publisher Correction: Semi-transparent graphite films growth on Ni and their double-sided polymer-free transfer.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Semi-transparent graphite films growth on Ni and their double-sided polymer-free transfer.

Nanorange thickness graphite films (NGFs) are robust nanomaterials that can be produced via catalytic chemical vapour deposition but questions remain regarding their facile transfer and how surface topography may affect their application in next-generation devices. Here, we report the growth of NGFs (with an area of 55 cm2 and thickness of ~ 100 nm) on both sides of a polycrystalline Ni foil and their polymer-free transfer (front- and back-side, in areas up to 6 cm2). Due to the catalyst foil topography, the two carbon films differed in physical properties and other characteristics such as surface roughness. We demonstrate that the coarser back-side NGF is well-suited for NO2 sensing, whereas the smoother and more electrically conductive front-side NGF (2000 S/cm, sheet resistance - 50 Ω/sq) could be a viable conducting channel or counter electrode in solar cells (as it transmits 62% of visible light). Overall, the growth and transfer processes described could help realizing NGFs as an alternative carbon material for those technological applications where graphene and micrometer-thick graphite films are not an option.

Organic field-effect transistor-based flexible sensors.

Flexible electronic devices have attracted a great deal of attention in recent years due to their flexibility, reduced complexity and lightweight. Such devices can conformably attach themselves to any bendable surface and can possess diverse transduction mechanisms. Consequently, with continued emphasis on innovation and development, major technological breakthroughs have been achieved in this area. This review focuses on the advancements of using organic field-effect transistors (OFETs) in flexible electronic applications in the past 10 years. In addition, to the above mentioned features, OFETs have multiple advantages such as low-cost, readout integration, large-area coverage, and power efficiency, which yield synergy. To begin with, we have introduced organic semiconductors (OSCs), followed by their applications in various device configurations and their mechanisms. Later, the use of OFETs in flexible sensor applications is detailed with multiple examples. Special attention is paid to discussing the effects induced on physical parameters of OFETs with respect to variations in external stimuli. The final section provides an outlook on the mechanical aspects of OSCs, activation and revival processes of sensory layers, small area analysis, and pattern recognition techniques for electronic devices.

Realization of an Ultrasensitive and Highly Selective OFET NO2 Sensor: The Synergistic Combination of PDVT-10 Polymer and Porphyrin-MOF.

Organic field-effect transistors (OFETs) are emerging as competitive candidates for gas sensing applications due to the ease of their fabrication process combined with the ability to readily fine-tune the properties of organic semiconductors. Nevertheless, some key challenges remain to be addressed, such as material degradation, low sensitivity, and poor selectivity toward toxic gases. Appropriately, a heterojunction combination of different sensing layers with multifunctional capabilities offers great potential to overcome these problems. Here, a novel and highly sensitive receptor layer is proposed encompassing a porous 3D metal-organic framework (MOF) based on isostructural-fluorinated MOFs acting as an NO2 specific preconcentrator, on the surface of a stable and ultrathin PDVT-10 organic semiconductor on an OFET platform. Here, with this proposed combination we have unveiled an unprecedented 700% increase in sensitivity toward NO2 analyte in contrast to the pristine PDVT-10. The resultant combination for this OFET device exhibits a remarkable lowest detection limit of 8.25 ppb, a sensitivity of 680 nA/ppb, and good stability over a period of 6 months under normal laboratory conditions. Further, a negligible response (4.232 nA/%RH) toward humidity in the range of 5%-90% relative humidity was demonstrated using this combination. Markedly, the obtained results support the use of the proposed novel strategy to achieve an excellent sensing performance with an OFET platform.

Fully Integrated Indium Gallium Zinc Oxide NO2 Gas Detector.

We report an amorphous indium gallium zinc oxide (IGZO)-based toxic gas detection system. The microsystem contains an IGZO thin-film transistor (TFT) as a sensing element and exhibits remarkable selectivity and sensitivity to low concentrations of nitrogen dioxide (NO2). In contrast to existing metal oxide-based gas sensors, which are active either at high temperature or with light activation, the developed IGZO TFT sensor is operable at room temperature and requires only visible light activation to revive the sensor after exposure to NO2. Furthermore, we demonstrate air-stable sensors with an experimental limit of detection of 100 ppb. This is the first report on metal oxide TFT gas sensors without heating or continuous light activation. Unlike most existing gas sensing systems that take care of identifying the analytes alone, the developed IGZO microsystem not only quantifies NO2 gas concentration but also yields a 5-bit digital output. The compact microsystem, incorporating readout and analog-to-digital conversion modules developed using only two TFTs, paves the way for inexpensive toxic gas monitoring systems.

Methanol and Humidity Capacitive Sensors Based on Thin Films of MOF Nanoparticles.

The successful development of modern gas sensing technologies requires high sensitivity and selectivity coupled to cost effectiveness, which implies the necessity to miniaturize devices while reducing the amount of sensing material. The appealing alternative of integrating nanoparticles of a porous metal-organic framework (MOF) onto capacitive sensors based on interdigitated electrode (IDE) chips is presented. We report the deposition of MIL-96(Al) MOF thin films via the Langmuir-Blodgett (LB) method on the IDE chips, which allowed the study of their gas/vapor sensing properties. First, sorption studies of several organic vapors like methanol, toluene, chloroform, etc. were conducted on bulk MOF. The sorption data revealed that MIL-96(Al) presents high affinity toward water and methanol. Later on, ordered LB monolayer films of MIL-96(Al) particles of ∼200 nm were successfully deposited onto IDE chips with homogeneous coverage of the surface in comparison to conventional thin film fabrication techniques such as drop-casting. The sensing tests showed that MOF LB films were selective for water and methanol, and short response/recovery times were achieved. Finally, chemical vapor deposition (CVD) of a porous thin film of Parylene C (thickness ∼250-300 nm) was performed on top of the MOF LB films to fabricate a thin selective layer. The sensing results showed an increase in the water selectivity and sensitivity, while those of methanol showed a huge decrease. These results prove the feasibility of the LB technique for the fabrication of ordered MOF thin films onto IDE chips using very small MOF quantities.

A chitosan gold nanoparticles molecularly imprinted polymer based ciprofloxacin sensor.

In this work, we present a novel study on the development of an electrochemical biomimetic sensor to detect the ciprofloxacin (CIP) antibiotic. A chitosan gold nanoparticles decorated molecularly imprinted polymer (Ch-AuMIP) was used to modify the glassy carbon electrode (GCE) for preparation of the sensor. The Ch-AuMIP was characterized to understand various properties like chemical composition, morphology, roughness, and conduction using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), atomic force microscopy (AFM) and cyclic voltammetry (CV) respectively. Several experimental conditions affecting the Ch-AuMIP/GCE sensor such as the CIP removal agent, the extraction time, the volume of Ch-AuMIP drop-cast onto GCE and the rebinding time were studied and optimized. The Ch-AuMIP sensor sensitivity was studied in the concentration range of 1-100 µmol L-1 exhibiting a limit of detection of 210 nmol L-1. The synergistic combination of Au nanoparticles and Ch-MIP helps detect the CIP antibiotic with good sensitivity and selectivity, respectively. We investigated the selectivity aspect by using some possible interfering species and the developed sensing system showed good selectivity for CIP with a 66% response compared to the other compounds (≤45% response). The proposed sensing strategy showed its applicability for successful detection of CIP in real samples like tap water, mineral water, milk, and pharmaceutical formulation. The developed sensor showed good selectivity towards CIP even among the analogue molecules of Norfloxacin (NFX) and Ofloxacin (OFX). The developed sensor was successfully applied to determine the CIP in different samples with a satisfactory recovery in the range of 94 to 106%.

Green and low-cost synthesis of zinc oxide nanoparticles and their application in transistor-based carbon monoxide sensing.

There has been steady progress in developing reliable and cost-effective strategies for the clean production of zinc oxide (ZnO) nanoparticles (NPs) owing to their unique structural and wide functional characteristics. While the green synthesis of such NPs from plant extracts has emerged as a sustainable and eco-friendly protocol, it is greatly restricted owing to the scarcity of potential natural precursors necessitating comprehensive investigations in this direction. Herein, we report a facile, low-cost green synthesis and characterization of ZnO NPs along with the demonstration of their usage as an active media in organic field-effect transistor (OFET) devices for sensing carbon monoxide (CO) gas. The ZnO NPs obtained from Nelumbo nucifera (lotus) leaf extract-mediated solution combustion synthesis at a much lower initiation temperature, the first of its kind, were characterized by various techniques such as UV-vis spectroscopy, XRD, EDX analysis, TEM and FESEM. The data derived from these experiments clearly evidence the formation of very pure and crystalline ZnO NPs possessing nearly spherical-shape with a size of 3-4 nm. The p-type organic field-effect transistor (OFET) device, fabricated using poly(3-hexylthiophene-2,5-diyl) (P3HT) and ZnO NPs, showed a field-effect mobility of 10-2 cm2 V-1 sec-1 with a slightly enhanced response of detecting CO gas at room temperature (RT). The phenomenon was further confirmed by the variation in electrical parameters of the OFET such as field-effect mobility (µ), on-current (I on), and off-current (I off). The selectivity and sensitivity of the fabricated device in CO gas detection was found to be more prominent than the other reducing gases (hydrogen sulphide, H2S and ammonia, NH3) and methanol vapours tested.

Ultra-sensitive gas phase detection of 2,4,6-trinitrotoluene by non-covalently functionalized graphene field effect transistors.

The high energy density (4.2 MJ kg-1) and low vapour pressure (7.2 × 10-9 atm) of chemical explosives such as TNT (2,4,6-trinitrotoluene) pose a grave security risk demanding immediate attention. Detection of such hazardous and highly challenging chemicals demands specific, ultra-sensitive and rapid detection platforms that can concomitantly transduce the signal as an electrical readout. Although chemo-sensitive strategies have been investigated, the majority of them are restricted to detecting TNT from solutions and are therefore not implementable in real-time, on-field situations. Addressing this demand, we report an ultra-sensitive (parts-per-billion) and rapid (∼40 s) detection platform for TNT based on non-covalently functionalized graphene field effect transistors (GFETs). This multi-parametric GFET detector exhibits a reliable and specific modulation in its Dirac point upon exposure to TNT in the vapour phase. The chemical specificity provided by 5-(4-hydroxyphenyl)-10,15,20-tri(p-tolyl) zinc porphyrin (ZnTTPOH) is synergistically combined with the high surface sensitivity of graphene through a non-covalent functionalization approach to realise p-doped GFETs (Zn-GFETs). Such a FET platform exhibits extremely sensitive shifts in Dirac point (ΔDP) that correlate with the number of nitro groups present in the analyte. Analytes with mono-, di-, and tri-nitro substituted aromatic molecules exhibit distinctly different ΔDP, leading to unprecedented specificity towards TNT. Additionally, the Dirac point of Zn-GFETs is invariant for common and potential interferons such as acetone and 2-propanol (perfume emulsifiers) thereby validating their practical applicability. Furthermore, the ΔDP is also manifested as changes in the contact potential of GFETs, indicating that sub-monolayer coverage of ZnTTPOH is sufficient to modulate the transfer characteristics of GFETs over an area 1000 times larger than the dopant dimensions. Specifically, ZnTTPOH-functionalized GFETs exhibit p-doped behaviour with positive ΔDP with respect to pristine GFETs. Such p-doped Zn-GFETs undergo selective charge-transfer mediated interactions with TNT resulting in enhanced electron withdrawal from Zn-GFETs. Thus the ΔDP shifts to a higher positive gate voltage leading to the dichotomous combination of the highest signal generation (1.2 × 1012 V mol-1) with ppb level molecular sensitivity. Significantly, the signal generated due to TNT is 105 times higher in magnitude compared to other potential interferons. The signal reliability is established in cross-sensitivity measurements carried out with a TNT-mDNB (1 : 10 molar ratio) mixture pointing to high specificity for immediate applications under atmospherically relevant conditions pertaining to homeland security and global safety.

A label-free aptasensor FET based on Au nanoparticle decorated Co3O4 nanorods and a SWCNT layer for detection of cardiac troponin T protein.

Acute myocardial infarction (AMI) is a serious health problem that must be identified in its early stages. Considerable progress has been made in understanding the condition of AMI through ascertaining the role of biomarkers, such as myoglobin, cardiac troponin proteins (T and I), creatine kinase-MB, and fatty acid-binding protein (FABP). A field-effect transistor (FET) is an effective platform; however, innovations are required in all layers of the FET for it to become robust and highly sensitive. For the first time, we made use of the synergistic combination of noble metal nanoparticles (AuNPs) with Co3O4 for the detection of cardiac troponin T (cTnT) in a FET platform. We determined the morphology of Au-decorated Co3O4 NRs and their electronic properties by characterizing the channel layer using electron microscopies and transient measurements. Subsequently, we performed the detection of cardiac troponin T by immobilizing its complementary biotinylated DNA aptamer on the channel surface using a drop-casting method. To understand the changes in drain current caused by this interaction, we probed our SWCNT-Co3O4 NR transistor with limited gate and drain bias (≤1 V), achieving a sensitivity of 0.5 µA µg-1 mL-1 for the Au-decorated NRs. A 250% increase in the sensitivity and a limit of detection (LOD) of 0.1 µg mL-1 were achieved by using this device. Finally, selectivity studies proved that this synergistic combination works well in the FET configuration for the successful detection of cTnT.

A Comparative Study of Interdigitated Electrode and Quartz Crystal Microbalance Transduction Techniques for Metal⁻Organic Framework-Based Acetone Sensors.

We present a comparative study of two types of sensor with different transduction techniques but coated with the same sensing material to determine the effect of the transduction mechanism on the sensing performance of sensing a target analyte. For this purpose, interdigitated electrode (IDE)-based capacitors and quartz crystal microbalance (QCM)-based resonators were coated with a zeolitic⁻imidazolate framework (ZIF-8) metal⁻organic framework thin films as the sensing material and applied to the sensing of the volatile organic compound acetone. Cyclic immersion in methanolic precursor solutions technique was used for depositing the ZIF-8 thin films. The sensors were exposed to various acetone concentrations ranging from 5.3 to 26.5 vol % in N2 and characterized/compared for their sensitivity, hysteresis, long-term and short-term stability, selectivity, detection limit, and effect of temperature. Furthermore, the IDE substrates were used for resistive transduction and compared using capacitive transduction.