Research Progress of Organic Field-Effect Transistor Based Chemical Sensors.

Due to their high sensitivity and selectivity, chemical sensors have gained significant attention in various fields, including drug security, environmental testing, food safety, and biological medicine. Among them, organic field-effect transistor (OFET) based chemical sensors have emerged as a promising alternative to traditional sensors, exhibiting several advantages such as multi-parameter detection, room temperature operation, miniaturization, flexibility, and portability. This review paper presents recent research progress on OFET-based chemical sensors, highlighting the enhancement of sensor performance, including sensitivity, selectivity, stability, etc. The main improvement programs are improving the internal and external structures of the device, as well as the organic semiconductor layer and dielectric structure. Finally, an outlook on the prospects and challenges of OFET-based chemical sensors is presented.

Polypyrrole Cubosomes with Ordered Ultralarge Mesopore for Controllable Encapsulation and Release of Albumin.

Despite substantial progress in porous materials over past years, controllable preparation of conductive polymers (CPs) with continuous large pores is challenging, which are important for diverse applications, including energy storage, electrocatalysis, and biological separations. Here, we develop an unprecedented ordered bicontinuous mesoporous PPy cubosomes (mPPy-cs) using a soft-template strategy, resulting in ultralarge pores of ∼45 nm and high specific surface area of 69.5 m2 g-1. Along with their unique characteristics of adjustable surface charges and sensitivity to pH, mPPy-cs exhibited a near quantitative adsorption of albumin within 30 min, enabling efficient separation from immunoglobulin G, a typical inclusion in commercial albumin products. Moreover, the absorbed albumin could be further released in a controlled manner by lowering the pH. This work provides a feasible strategy for bottom-up construction of CPs with tailored pore sizes and nanoarchitectures, expected to attract significant attention to their properties and applications.

In Situ Turn-On Room Temperature Phosphorescence and Vapor Ultra-sensitivity at Lifetime Mode.

Organic room temperature phosphorescence (RTP) systems are rarely reported for vapor phase sensing due to the contradiction between vapor permeability and phosphorescence ability. Till now, almost all reported works are based on ″turn-off″ mode RTP detection by destroying the compact-packaging oxygen-free environment. ″Turn-on″ mode RTP detection owns additional anti-interference capability due to a lower initial RTP background signal, while its realization is even harder. In this research, in situ phosphorescence ″turn-on″ sensing was realized for methamphetamine (MPEA) vapor detection. Based on the formation of aromatic phenolic aldehyde-secondary amine ion pairs with air-stable RTP performance, the fluorescent tri-formyl phenol (TFP) film was converted into a stable RTP state after being exposed to the MPEA vapor, as supported by nuclear magnetic resonance (NMR) and mass spectrometry together with theoretical calculations. The red-shifted absorption and emission, enhanced emission intensity, and 49.7 µs phosphorescence lifetime allowed multiple mode MPEA vapor sensing from chromaticity to fluorescence to phosphorescence. The lifetime mode detection limit reached 0.4 ppt, 5 orders of magnitude lower than the intensity mode detection limit of 20.3 ppb.

Controlled Synthesis of Mesoporous π-Conjugated Polymer Nanoarchitectures as Anodes for Lithium-Ion Batteries.

Conjugated polymers possess better electron conductivity due to large π-electron conjugated configuration endowing them significant scientific and technological interest. However, the obvious deficiency of active-site underutilization impairs their electrochemical performance. Therefore, designing and engineering π-conjugated polymers with rich redox functional groups and mesoporous architectures could offer new opportunities for them in these emerging applications and further expand their application scopes. Herein, a series of 1,3,5-tris(4-aminophenyl) benzene (TAPB)-based π-conjugated mesoporous polymers (π-CMPs) are constructed by one-pot emulsion-induced interface assembly strategy. Furthermore, co-induced in situ polymerization on 2D interfaces by emulsion and micelles is explored, which delivers sandwiched 2D mesoporous π-CMPs-coated graphene oxides (GO@mPTAPB). Benefiting from specific redox-active functional groups, excellent electron conductivity and a 2D mesoporous conjugated framework, GO@mPTAPB exhibits high capability of accommodating Li+ anions (up to 382 mAh g-1 at 0.2 A g-1 ) and outstanding electrochemical stability (87.6% capacity retention after 1000 cycles). The ex situ Raman and impedance spectra are further applied to reveal the high reversibility of GO@mPTAPB. This work will greatly promote the development of advanced π-CMPs-based organic anodes toward energy storage devices.

General Construction of 2D Ordered Mesoporous Iron-Based Metal-Organic Nanomeshes.

Nanomeshes with highly regular, permeable pores in plane, combining the exceptional porous architectures with intrinsic properties of 2D materials, have attracted increasing attention in recent years. Herein, a series of 2D ultrathin metal-organic nanomeshes with ordered mesopores is obtained by a self-assembly method, including metal phosphate and metal phosphonate. The resultant mesoporous ferric phytate nanomeshes feature unique 2D ultrathin monolayer morphologies (≈9 nm thickness), hexagonally ordered, permeable mesopores of ≈16 nm, as well as improved surface area and pore volume. Notably, the obtained ferric phytate nanomeshes can directly in situ convert into mesoporous sulfur-doped metal phosphonate nanomeshes by serving as an unprecedented reactive self-template. Furthermore, as advanced anode materials for Li-ion batteries, they deliver excellent capacity, good rate capability, and cycling performance, greatly exceeding the similar metal phosphate-based materials reported previously, resulting from their unique 2D ultrathin mesoporous structure. Therefore, the work will pave an avenue for constructing the other 2D ordered mesoporous materials, and thus offer new opportunities for them in diverse areas.

Pre-Polymerization Enables Controllable Synthesis of Nanosheet-Based Porphyrin Polymers towards High-Performance Li-Ion Batteries.

The precise regulation of nucleation growth and assembly of polymers is still an intriguing goal but an enormous challenge. In this study, we proposed a pre-polymerization strategy to regulate the assembly and growth of polymers by facilely controlling the concentration of polymerization initiator, and thus obtained two kinds of different nanosheet-based porphyrin polymer materials using tetrakis-5,10,15,20-(4-aminophenyl) porphyrin (TAPP) as the precursor. Notably, due to the π-π stacking and doping of TAPP during the preparation process, the obtained PTAPP-nanocube material exhibits a high intrinsic bulk conductivity reaching 1.49×10-4  S m-1 . Profiting from the large π-conjugated structure of porphyrin units, closely stacked layer structure and excellent conductivity, the resultant porphyrin polymers, as electrode materials for lithium ion batteries, deliver high specific capacity (≈650 mAh g-1 at the current density of 100 mA g-1 ), excellent rate performance and long-cycle stability, which are among the best reports of porphyrin polymer-based electrode materials for lithium-ion batteries, to the best of our knowledge. Therefore, such a pre-polymerization approach would provide a new insight for the controllable synthesis of polymers towards custom-made architecture and function.

Self-Stabilized Amorphous Organic Materials with Room-Temperature Phosphorescence.

The stability of pure organic room-temperature phosphorescent (RTP) materials in air has been a research hotspot in recent years. Without crystallization or encapsulation, a new strategy was proposed to obtain self-stabilized organic RTP materials, based on a complete ionization of a photo-induced charge separation system. The ionization of aromatic phenol 4-carbazolyl salicylaldehyde (CSA) formed a stable H-bonding anion-cation radical structure and led to the completely amorphous CSA-I film. Phosphorescent lifetimes as long as 0.14 s at room temperature and with direct exposure to air were observed. The emission intensity was also increased by 21.5-fold. Such an amorphous RTP material reconciled the contradiction between phosphorescence stability and vapor permeability and has been successfully utilized for peroxide vapor detection.

Attogram "Meth" Detection Enabled by Selective Organic Crystal Disaggregation via Directed Crystal Level Interactions.

In this contribution, completely different from traditional probes based on molecular host-guest interaction, crystal level interaction was proposed as an ultrasensitive design strategy for molecule detection. In such a strategy, crystal-guest interaction triggered rapid crystal disaggregation to gain great signal change, far more efficient than molecule scale coupling. Highly ordered pyrene methanol (PM) crystal was self-assembled with hydrogen bond chain and π-π stacking force. Its {011} surface can be destabilized by methamphetamine hydrochlorate (MA, heavily used illicit drug) selectively and efficiently. The detection limit was improved to an amazing attogram level (5.4 ag/mL, 29.1 fM), 9 orders of magnitude lower than the best reported host-guest result.

Schiff Base Substituent-Triggered Efficient Deboration Reaction and Its Application in Highly Sensitive Hydrogen Peroxide Vapor Detection.

The organic thin-film fluorescence probe, with the advantages of not polluting the analyte and fast response, has attracted much attention in explosive detection. Different with nitro explosives, the peroxide-based explosives are hardly to be detected because of their poor ultraviolet absorption and lack of an aromatic ring. As the signature compound of peroxide-based explosives, H2O2 vapor detection became more and more important. Boron ester or acid is considered to be a suitable functional group for the detection of hydrogen peroxide due to its reliable reactive activity. Its only drawback lies on its slow degradation velocity. In this work, we try to introduce some functional group to make the boron ester to be easily oxidized by H2O2. Herein, 4-(phenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amino)benzaldehyde (OTB) was synthesized and its imine derivatives, OTBXAs, were easily obtained just by putting OTB films in different primary amines vapors. OTBXAs show fast deboronation velocity in H2O2 vapor compared with OTB. The complete reaction time of (E)-N-phenyl-4-((propylimino)methyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline (OTBPA) was even shortened 40 times with a response time of seconds. The detection limit for H2O2 vapor was as low as 4.1 parts per trillion (ppt). Further study showed that it is a general approach to enhance the sensing performance of borate to hydrogen peroxide (H2O2) vapor by introducing an imine into an aromatic borate molecule via a solid/vapor reaction.

Concise and Efficient Fluorescent Probe via an Intromolecular Charge Transfer for the Chemical Warfare Agent Mimic Diethylchlorophosphate Vapor Detection.

Sarin, used as chemical warfare agents (CWAs) for terrorist attacks, can induce a number of virulent effects. Therefore, countermeasures which could realize robust and convenient detection of sarin are in exigent need. A concise charge-transfer colorimetric and fluorescent probe (4-(6-(tert-butyl)pyridine-2-yl)-N,N-diphenylaniline, TBPY-TPA) that could be capable of real-time and on-site monitoring of DCP vapor was reported in this contribution. Upon contact with DCP, the emission band red-shifted from 410 to 522 nm upon exposure to DCP vapor. And the quenching rate of TBPY-TPA reached up to 98% within 25 s. Chemical substances such as acetic acid (HAc), dimethyl methylphosphonate (DMMP), pinacolyl methylphosphonate (PAMP), and triethyl phosphate (TEP) do not interfere with the detection. A detection limit for DCP down to 2.6 ppb level is remarkably achieved which is below the Immediately Dangerous to Life or Health concentration. NMR data suggested that a transformation of the pyridine group into pyridinium salt via a cascade reaction is responsible for the sensing process which induced the dramatic fluorescent red shift. All of these data suggest TBPY-TPA is a promising fluorescent sensor for a rapid, simple, and low-cost method for DCP detection, which could be easy to prepare as a portable chemosensor kit for its practical application in real-time and on-site monitoring.

Direct Active Site at the Van der Waals Heterostructure Interface with Synthetic Drug Analogue N-Methylphenethylimine Ultrasensitivity.

CNT/organic probe-based chemiresistive sensors suffer from the problem of low sensitivity and poor stability due to the unstable and unfavorable CNT/organic probe interface. A new designing strategy of a one-dimensional van der Waals heterostructure was developed for ultrasensitive vapor sensing. By modifying the perylene diimide molecule at the bay region with phenoxyl and further Boc-NH- phenoxy side chains, a highly stable 1D VDW heterostructure SWCNT-probe molecule system was formed with ultrasensitivity and specificity. Interfacial recognition sites consisting of SWCNT and the probe molecule are responsible for the synergistical and excellent sensing response to MPEA molecules, which was proved by Raman, XPS, and FTIR characterizations together with dynamic simulation. Based on such a sensitive and stable VDW heterostructure system, the measured detection limit reached as low as 3.6 ppt for the synthetic drug analogue N-methylphenethylimine (MPEA) in the vapor phase, and the sensor showed almost no performance degradation even after 10 days. Furthermore, a miniaturized detector was developed for real-time monitoring of drug vapor detection.

Tuning electron delocalization of hydrogen-bonded organic framework cathode for high-performance zinc-organic batteries.

Stable cathodes with multiple redox-active centres affording a high energy density, fast redox kinetics and a long life are continuous pursuits for aqueous zinc-organic batteries. Here, we achieve a high-performance zinc-organic battery by tuning the electron delocalization within a designed fully conjugated two-dimensional hydrogen-bonded organic framework as a cathode material. Notably, the intermolecular hydrogen bonds endow this framework with a transverse two-dimensional extended stacking network and structural stability, whereas the multiple C = O and C = N electroactive centres cooperatively trigger multielectron redox chemistry with super delocalization, thereby sharply boosting the redox potential, intrinsic electronic conductivity and redox kinetics. Further mechanistic investigations reveal that the fully conjugated molecular configuration enables reversible Zn2+/H+ synergistic storage accompanied by 10-electron transfer. Benefitting from the above synergistic effects, the elaborately tailored organic cathode delivers a reversible capacity of 498.6 mAh g-1 at 0.2 A g-1, good cyclability and a high energy density (355 Wh kg-1).

Solution-based self-assembly synthesis of two-dimensional-ordered mesoporous conducting polymer nanosheets with versatile properties.

Conducting polymers with conjugated backbones have been widely used in electrochemical energy storage, catalysts, gas sensors and biomedical devices. In particular, two-dimensional (2D) mesoporous conducting polymers combine the advantages of mesoporous structure and 2D nanosheet morphology with the inherent properties of conducting polymers, thus exhibiting improved electrochemical performance. Despite the use of bottom-up self-assembly approaches for the fabrication of a variety of mesoporous materials over the past decades, the synchronous control of the dimensionalities and mesoporous architectures for conducting polymer nanomaterials remains a challenge. Here, we detail a simple, general and robust route for the preparation of a series of 2D mesoporous conducting polymer nanosheets with adjustable pore size (5-20 nm) and thickness (13-45 nm) and controllable morphology and composition via solution-based self-assembly. The synthesis conditions and preparation procedures are detailed to ensure the reproducibility of the experiments. We describe the fabrication of over ten high-quality 2D-ordered mesoporous conducting polymers and sandwich-structured hybrids, with tunable thickness, porosity and large specific surface area, which can serve as potential candidates for high-performance electrode materials used in supercapacitors and alkali metal ion batteries, and so on. The preparation time of the 2D-ordered mesoporous conducting polymer is usually no more than 12 h. The subsequent supercapacitor testing takes ~24 h and the Na ion battery testing takes ~72 h. The procedure is suitable for users with expertise in physics, chemistry, materials and other related disciplines.

Directional Activated Exciton Highway via Fractal Electric Field Modulation for Ultrasensitive Carbon Nanotube-Based Sensors.

The electrical vapor sensor based on carbon nanotubes (CNTs) has attracted wide attention due to its excellent conductivity, stable interfacial structure, and low dimensional quantum effects. However, the conductivity and contact interface activity were still limited by the random distribution of coated CNTs, which led to limited performance. We developed a new strategy to unify the CNT directions with image fractal designing of the electrode system. In such a system, directional aligned CNTs were gained under a well-modulated electric field, leading to microscale CNT exciton highways and molecule-scale host-guest site activation. The carrier mobility of the aligned CNT device is 20-fold higher than that of the random network CNT device. With excellent electrical properties, such modulated CNT devices based on fractal electrodes behave as an ultrasensitive vapor sensor for methylphenethylamine, a mimic of illicit drug methamphetamine. The detection limit reached as low as 0.998 ppq, 6 orders of magnitude sensitive than the reported 5 ppb record based on interdigital electrodes with random distributed CNTs. Since the device is easily fabricated in wafer-level and compatible with the CMOS process, such a fractal design strategy for aligned CNT preparation will be widely applied in a variety of wafer-level electrical functional devices.

A Universal Microscopic Patterned Doping Method for Perovskite Enables Ultrafast, Self-Powered, Ultrasmall Perovskite Photodiodes.

Novel metal halide perovskite is proven to be a promising optoelectronic material. However, fabricating microscopic perovskite devices is still challenging because the perovskite is soluble with the photoresist, which conflicts with conventional microfabrication technology. The size of presently reported perovskite devices is about 50 µm. Limited by the large size of perovskite optoelectronic devices, they cannot be readily adopted in the fields of imaging, display, etc. Herein a universal microscopic patterned doping method is proposed, which can realize microscale perovskite devices. Rather than by the conventional doping method, in this study the local Fermi level of perovskite is modulated by the redistributing intrinsic ion defects via a polling voltage. A satisfactorily stable polarized ion distribution can be achieved by optimization of the perovskite material and polling voltage, resulting in ultrafast (40 µs), self-powered microscale (2 µm) photodiodes. This work sheds light on a route to fabricate integrated perovskite optoelectronic chips.

Polyoxometalate-Bridged Synthesis of Superstructured Mesoporous Polymers and Their Derivatives for Sodium-Iodine Batteries.

Despite the impressive progress in mesoporous materials over past decades, for those precursors having no well-matched interactions with soft templates, there are still obstacles to be guided for mesoporous structure via soft-template strategies. Here, a polyoxometalate-assisted co-assembly route is proposed for controllable construction of superstructured mesoporous materials by introducing polyoxometalates as bifunctional bridge units, which weakens the self-nucleation tendency of the precursor through coordination interactions and simultaneously connects the template through the induced dipole-dipole interaction. By this strategy, a series of meso-structured polymers, featuring highly open radial mesopores and dendritic pore walls composed of continuous interwoven nanosheets can be facilely obtained. Further carbonization gave rise to nitrogen-doped hierarchical mesoporous carbon decorated uniformly with ultrafine γ-Mo2 N nanoparticles. Density functional theory proves that nitrogen-doped carbon and γ-Mo2 N can strongly adsorb polyiodide ions, which effectively alleviate polyiodide dissolving in organic electrolytes. Thereby, as the cathode materials for sodium-iodine batteries, the I2 -loaded carbonaceous composite shows a high specific capacity (235 mA h g-1 at 0.5 A g-1 ), excellent rate performance, and cycle stability. This work will open a new venue for controllable synthesis of new hierarchical mesoporous functional materials, and thus promote their applications toward diverse fields.

Realization of high-dynamic-range broadband magnetic-field sensing with ensemble nitrogen-vacancy centers in diamond.

We present a new magnetometry method integrating an ensemble of nitrogen-vacancy (NV) centers in a single-crystal diamond with an extended dynamic range for monitoring a fast changing magnetic-field. The NV-center spin resonance frequency is tracked using a closed-loop frequency locked technique with fast frequency hopping to achieve a 10 kHz measurement bandwidth, thus allowing for the detection of fast changing magnetic signals up to 0.723 T/s. This technique exhibits an extended dynamic range subjected to the working bandwidth of the microwave source. This extended dynamic range can reach up to 4.3 mT, which is 86 times broader than the intrinsic dynamic range. The essential components for NV spin control and signal processing, such as signal generation, microwave frequency control, data processing, and readout, are integrated in a board-level system. With this platform, we demonstrate a broadband magnetometry with an optimized sensitivity of 4.2 nT Hz-1/2. This magnetometry method has the potential to be implemented in a multichannel frequency locked vector magnetometer suitable for a wide range of practical applications, such as magnetocardiography and high-precision current sensors.

Mesoporous Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) as Efficient Iodine Host for High-Performance Zinc-Iodine Batteries.

Here, by introducing polystyrenesulfonate (PSS) as a multifunctional bridging molecule to synchronously coordinate the interaction between the precursor and the structure-directing agent, we developed a mesoporous conductive polymer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) featuring adjustable size in the range of 105-1836 nm, open nanochannels, large specific surface area (105.5 m2 g-1), and high electrical conductivity (172.9 S cm-1). Moreover, a large-area ultrathin PEDOT:PSS thin film with well-defined mesopores can also be obtained by controllable growth on various functional interfaces. As an example, we demonstrated that the iodine-loaded mesoporous PEDOT:PSS nanospheres can serve as a promising cathode for aqueous zinc-iodine batteries with high specific capacity (241 mAh g-1), excellent rate performance, and superlong 20,000 cycle life. In-depth theoretical calculations and systematic experimental results together reveal that the exposed sulfur- and oxygen-containing functional groups hold strong interactions with iodine species, resulting in effectively anchoring iodine species and inhibiting the shuttling of polyiodide intermediates, thus ensuring the long-term stability of the batteries. This work introduces a member to the family of mesoporous materials as well as porous polymers with versatile applications.

Interface Influence on the Photoelectric Performance of Transition Metal Dichalcogenide Lateral Heterojunctions.

The ultrathin feature of two-dimensional (2D) transition metal dichalcogenides (TMDs) has brought special performance in electronic and optoelectronic fields. When vertical and lateral heterojunctions are made using different TMD combinations, the original properties of premier TMDs can be optimized. Especially for lateral heterojunctions, their sharp interface signifies a narrow space charge region, leading to a strong in-plane built-in electric field, which may contribute to high separation efficiency of photogenerated carriers, good rectification behavior, self-powered photoelectric device construction, etc. However, due to the poor controllability over the synthesis process, obtaining a clean and sharp interface of the lateral heterojunction is still a challenge. Herein, we propose a simple chemical vapor deposition (CVD) method, which can effectively separate the growth process of different TMDs, thus resulting in good regulation of the composition change at the junction region. By this method, MoS2-WS2 lateral heterojunctions with sharp interfaces have been obtained with good rectification characteristics, ∼105 on/off ratio, 1874% external quantum efficiency, and ∼120 ms photoresponse speed, exhibiting a better photoelectric performance than that of the lateral ones with graded junctions.

Supramolecule-Originated Emission: A Room-Temperature Phosphorescence 2D Ionic H-Bond Network from Nonemissive Aliphatic Derivatives.

Supramolecular materials exhibiting unique functions unavailable from their individual components are attracting great attention. Here, we report a novel supramolecule emission strategy, where the emission originated from a two-dimensional (2D) ionic hydrogen bond (H-bond) supramolecular network. High-quality crystals were obtained by rapid self-assembly of liquid aliphatic amine and ketone. The 2D ionic H-bonding network was characterized by single-crystal X-ray diffraction (XRD) that shows a planar electron system similar to aromatic species. First-principles calculations demonstrated that the charge-separated transition process and high spin-orbital coupling constants of the rigid supramolecular structure contribute to the enhanced singlet-triplet intersystem crossing process. The emission could be well regulated via the substituents of either the enol or amine part, and a maximum quantum efficiency of 26% was realized. The emission system demonstrated stable room-temperature phosphorescence (RTP), which is even hard to obtain for aromatic species, and the lifetime reached 0.45 s with an 8% luminescence quantum yield. For application, with liquid amine and enol as ink, high-quality RTP patterns can be fabricated by computer-controlled precision printing. Our findings will surely bring completely fresh thinking for photoluminescence and other functions purely originated by the supramolecular structure.