Perovskite Solar Cell-Gated Organic Electrochemical Transistors for Flexible Photodetectors with Ultrahigh Sensitivity and Fast Response.

Photodetectors (PDs) are the building block of various imaging and sensing applications. However, commercially available PDs based on crystalline inorganic semiconductors cannot meet the requirements of emerging wearable/implantable applications due to their rigidity and fragility, which creates the need for flexible devices. Here, a high-performance flexible PD is presented by gating an organic electrochemical transistor (OECT) with a perovskite solar cell. Due to the ultrahigh transconductance of the OECT, the device demonstrates a high gain of ≈106 , a fast response time of 67 µs and an ultrahigh detectivity of 6.7 × 1017 Jones to light signals under a low working voltage (≤0.6 V). Thanks to the ultrahigh sensitivity and fast response, the device can track photoplethysmogram signals and peripheral oxygen saturation under ambient light and even provide contactless remote sensing, offering a low-power and convenient way for continuous vital signs monitoring. This work offers a novel strategy for realizing high-performance flexible PDs that are promising for low-power, user-friendly and wearable optoelectronics.

Ultrasensitive Detection of Ribonucleic Acid Biomarkers Using Portable Sensing Platforms Based on Organic Electrochemical Transistors.

The analysis of ribonucleic acid (RNA) plays an important role in the early diagnosis of diseases and will greatly benefit patients with a higher cure rate. However, the low abundance of RNA in physiological environments requires ultrahigh sensitivity of a detection technology. Here, we construct a portable and smart-phone-controlled biosensing platform based on disposable organic electrochemical transistors for ultrasensitive analysis of microRNA (miRNA) biomarkers within 1 h. Due to their inherent amplification function, the devices can detect miRNA cancer biomarkers from little-volume solutions with concentrations down to 10-14 M. The devices can distinguish blood miRNA expression levels at different cancer stages using a 4T1 mouse tumor model. The technique for ultrasensitive and fast detection of RNA biomarkers with high selectivity opens a window for mobile diagnosis of various diseases with low cost.

Ultrafast, sensitive, and portable detection of COVID-19 IgG using flexible organic electrochemical transistors.

The outbreak of COVID-19 and its continued spread have seriously threatened public health. Antibody testing is essential for infection diagnosis, seroepidemiological analysis, and vaccine evaluation. However, convenient, fast, and accurate antibody detection remains a challenge in this protracted battle. Here, we report an ultrafast, low-cost, label-free, and portable SARS-CoV-2 immunoglobulin G (IgG) detection platform based on organic electrochemical transistors (OECTs), which can be remotely controlled by a mobile phone. To enable faster detection, voltage pulses are applied on the gate electrode of the OECT to accelerate binding between the antibody and antigen. By optimizing ion concentrations and pH values of test solutions, we realize specific detection of SARS-CoV-2 IgG in several minutes with a detectable region from 10 fM to 100 nM, which encompasses the range of serum SARS-CoV-2 IgG levels in humans. These portable sensors show promise for use in diagnosis and prognosis of COVID-19.

Highly sensitive detection of caspase-3 activity based on peptide-modified organic electrochemical transistor biosensors.

Caspase-3 is an important proteolytic enzyme that cleaves several key substrates in apoptotic processes, resulting in DNA fragmentation, the degradation of nuclear proteins, and the formation of apoptotic bodies. However, it is challenging to detect caspase-3 due to its low expression levels in cells. In this work, organic electrochemical transistors (OECTs) are used in the detection of caspase-3 for the first time. A self-assembled monolayer of the peptide is bonded to the Au gate electrode (GE) of an OECT via gold-sulphur bonds. It is found that the transfer curve of the transistor shifts to a lower gate voltage due to the modulation of the surface potential of the GE by the peptides. Then, the device is used in the detection of caspase-3 in aqueous solutions and shows a detection limit of 0.1 pM. Due to its high sensitivity, the device can detect caspase-3 in induced apoptotic HeLa cells. The system is low-cost, conveniently used and applicable for biological and medical monitoring where caspase-3 detection and quantification are required.

Solution-Phase Epitaxial Growth of Perovskite Films on 2D Material Flakes for High-Performance Solar Cells.

The quality of perovskite films is critical to the performance of perovskite solar cells. However, it is challenging to control the crystallinity and orientation of solution-processed perovskite films. Here, solution-phase van der Waals epitaxy growth of MAPbI3 perovskite films on MoS2 flakes is reported. Under transmission electron microscopy, in-plane coupling between the perovskite and the MoS2 crystal lattices is observed, leading to perovskite films with larger grain size, lower trap density, and preferential growth orientation along (110) normal to the MoS2 surface. In perovskite solar cells, when perovskite active layers are grown on MoS2 flakes coated on hole-transport layers, the power conversion efficiency is substantially enhanced for 15%, relatively, due to the increased crystallinity of the perovskite layer and the improved hole extraction and transfer rate at the interface. This work paves a way for preparing high-performance perovskite solar cells and other optoelectronic devices by introducing 2D materials as interfacial layers.

Functionalized Organic Thin Film Transistors for Biosensing.

The rise of organic bioelectronics efficiently bridges the gap between semiconductor devices and biological systems, leading to flexible, lightweight, and low-cost organic bioelectronic devices suitable for health or body signal monitoring. The introduction of organic semiconductors in the devices can soften the boundaries between microelectronic systems and dynamically active cells and tissues. Therefore, organic bioelectronics has attracted much attention recently due to the unique properties and promising applications. Organic thin film transistors (OTFTs), owing to their inherent capability of amplifying received signals, have emerged as one of the state-of-the-art biosensing platforms. The advantages of organic semiconductors in terms of synthetic freedom, low temperature solution processing, biocompatibility, and mechanical flexibility render OTFTs ideal transducers for wearable electronics, e-skin, and implantable devices. How to realize highly sensitive, selective, rapid, and efficient signal capture and extraction of biological recognition events is the major challenge in the design of biosensors. OTFTs are prone to converting the presence or change of target analytes into specific electrical signals even in complex biological systems. More importantly, OTFT sensors can be conveniently functionalized with chemical or biological modifications and exhibit substantially improved device sensitivity and selectivity as well as other analytical figure of merits, including calibration range, linearity, and accuracy. However, the stability and reproducibility of the organic devices need to be further improved. In this Account, we first introduce the unique features of OTFTs for bioelectronic applications. Two typical OTFT configurations, including organic electrochemical transistor (OECT) and electrolyte gated organic field effect transistor (EGOFET), are highlighted in their sensing applications mainly due to the operation of the devices in electrolytes and the combination of ionic and electronic charge transports in the devices. These devices are potentiometric transducers with low working voltages (<1 V) and high sensitivity, and are thus suitable for wearable applications with low power consumption. Second, the functionalization strategies on channel materials, electrolytes, and gate electrodes based on various modification methods and sensing mechanisms are discussed in sequence. In an OECT- or EGOFET-based biosensor, the device performance is particularly sensitive to the physical properties of the two interfaces, including channel/electrolyte and gate/electrolyte interfaces. Any change in the potential drop or capacitance of either interface can influence the channel current substantially. Therefore, the functionalization of the interfaces is critical to the sensing performance. In particular, when an electrochemically active material is modified on the interfaces, the reaction of the analyte catalyzed by the modified material can influence the interface potential and lead to a channel current response much stronger than that of a conventional electrochemical measurement. So the biosensors are much more sensitive than typical analytical methods due to the signal amplification of the transistors. Third, the processing techniques including screen printing and inkjet printing and the possibility for mass production are discussed. The applications of organic transistors in wearable electronics and healthcare monitoring systems, especially the fabric OECT-based biosensors for noninvasive detection, are presented. It is expected that the versatile organic transistors will enable various compact, flexible and disposable biosensors compatible with wearable electronics.

Fabric Organic Electrochemical Transistors for Biosensors.

Flexible fabric biosensors can find promising applications in wearable electronics. However, high-performance fabric biosensors have been rarely reported due to many special requirements in device fabrication. Here, the preparation of organic electrochemical transistors (OECTs) on Nylon fibers is reported. By introducing metal/conductive polymer multilayer electrodes on the fibers, the OECTs show very stable performance during bending tests. The devices with functionalized gates are successfully used as various biosensors with high sensitivity and selectivity. The fiber-based OECTs are woven together with cotton yarns successfully by using a conventional weaving machine, resulting in flexible and stretchable fabric biosensors with high performance. The fabric sensors show much more stable signals in the analysis of moving aqueous solutions than planar devices due to a capillary effect in fabrics. The fabric devices are integrated in a diaper and remotely operated by using a mobile phone, offering a unique platform for convenient wearable healthcare monitoring.

Organic Electrochemical Transistors for the Detection of Cell Surface Glycans.

Cell surface glycans play critical roles in diverse biological processes, such as cell-cell communication, immunity, infection, development, and differentiation. Their expressions are closely related to cancer growth and metastasis. This work demonstrates an organic electrochemical transistor (OECT)-based biosensor for the detection of glycan expression on living cancer cells. Herein, mannose on human breast cancer cells (MCF-7) as the target glycan model, poly dimethyl diallyl ammonium chloride-multiwall carbon nanotubes (PDDA-MWCNTs) as the loading interface, concanavalin A (Con A) with active mannose binding sites, aptamer and horseradish peroxidase co-immobilized gold nanoparticles (HRP-aptamer-Au NPs) as specific nanoprobes are used to fabricate the OECT biosensor. In this strategy, PDDA-MWCNT interfaces can enhance the loading of Con A, and the target cells can be captured through Con A via active mannose binding sites. Thus, the expression of cell surface can be reflected by the amount of cells captured on the gate. Specific nanoprobes are introduced to the captured cells to produce an OECT signal because of the reduction of hydrogen peroxide catalyzed by HRP conjugated on Au nanoparticles, while the aptamer on nanoprobes can selectively recognize the MCF-7 cells. It is reasonable that more target cells are captured on the gate electrode, more HRP-nanoprobes are loaded thus a larger signal response. The device shows an obvious response to MCF-7 cells down to 10 cells/µL and can be used to selectively monitor the change of mannose expression on cell surfaces upon a treatment with the N-glycan inhibitor. The OECT-based biosensor is promising for the analysis of glycan expressions on the surfaces of different types of cells.

Highly Sensitive Detection of Protein Biomarkers with Organic Electrochemical Transistors.

The analysis of protein biomarkers is of great importance in the diagnosis of diseases. Although many convenient and low-cost electrochemical approaches have been extensively investigated, they are not sensitive enough in the detection of protein biomarkers with low concentrations in physiological environments. Here, this study reports a novel organic-electrochemical-transistor-based biosensor that can successfully detect cancer protein biomarkers with ultrahigh sensitivity. The devices are operated by detecting electrochemical activity on gate electrodes, which is dependent on the concentrations of proteins labeled with catalytic nanoprobes. The protein sensors can specifically detect a cancer biomarker, human epidermal growth factor receptor 2, down to the concentration of 10-14 g mL-1 , which is several orders of magnitude lower than the detection limits of previously reported electrochemical approaches. Moreover, the devices can successfully differentiate breast cancer cells from normal cells at various concentrations. The ultrahigh sensitivity of the protein sensors is attributed to the inherent amplification function of the organic electrochemical transistors. This work paves a way for developing highly sensitive and low-cost biosensors for the detection of various protein biomarkers in clinical analysis in the future.

Enhancement of neurite adhesion, alignment and elongation on conductive polypyrrole-poly(lactide acid) fibers with cell-derived extracellular matrix.

Extracellular matrix (ECM) can promote peripheral nerve repair. In this study, a conductive fiber-film (CFF) with core-sheath structure and conductivity of ∼10Scm-1 was prepared by electrospinning of aligned poly(l-lactide acid) (PLLA) fibers and electrochemical deposition of polypyrole (PPy) nanoparticles. Then the multiple components of ECM, including laminin, fibronectin and collagen, were coated on the surface of CFF by culturing and lysing L929 cells to fabricate the bioactive scaffold of ECM-linked CFF (ECM-CFF). The electrical stimulation (ES) of 100mV/cm for 14days and 2h per day did not significantly decrease the conductivity of ECM-CFF. The results of PC12 cells test indicated that, cells adhesion rate, neurite-bearing cell rate and neurite alignment rate on ECM-CFF were ∼95%, ∼77%, ∼70%, respectively, significantly larger than the corresponding values on bare CFF (17%, 29% and 14%, respectively). The neurites length on ECM-CFF (∼79mm) was also larger than that on bare CFF (∼25mm). ES of 100mV/cm onto PC12 cells through ECM-CFF could significantly promote neurite extension in first 3days of the neurite growth. These results indicated that, the combination of ECM-CFF with ES could improve the nerve regeneration by encouraging neural-cell adhesion, neurite growth and extension.

Fabrication and Protein Conjugation of Aligned Polypyrrole-Poly(L-lactic acid) Fibers Film with the Conductivity and Stability.

The conducting composite scaffold, including fiber-cores of aligned poly(L-lactic acid) (PLLA) and shell-layer of polypyrrole (PPy), was fabricated, and then bovine serum albumin (BSA) was conjugated on the PPy shell-layer. Aligned PLLA fibers (about 300 nm diameter) were obtained by electrospinning and rotating drum collection, and then coated by PPy nanoparticles (NPs, about 50 nm diameter) via chemical oxidation. The surface resistivity of PPy-PLLA fibers film were 0.971, 0.874 kΩ. cm at the fiber's vertical and parallel directions, respectively. The results of PPy-PLLA fibers film immersed in phosphate buffer saline for 8 d indicated that the fibers morphology and the film conductivity were not significantly changed, and the fluorescent images showed that FITC-labeled BSA (FITC-BSA) were successfully conjugated in the fibers film with carbodiimide chemistry, and the largest amount of FITC-BSA conjugated in the fibers film from 100 µg/mL proteins solution was 31.31 µg/cm2 due to lots of poly(glutamic acid) in surface-nanogrooves of the fibers surface. Under electrical stimulation of 100 mV, the fibers film was accompanied the release of all conjugated FITC-BSA with the detachment of some PPy NPs. These results suggested that PPy-PLLA fibers film would be potentially applied in the construction of degradable tissue engineering scaffold with protein factors, especially neurotrophic factors for nerve tissue repair.

Fabrication of aligned, porous and conductive fibers and their effects on cell adhesion and guidance.

The potential applications of aligned, conductive electrospun fibers have been widely studied in anisotropic tissue regeneration. In this study, aligned porous poly L-lactic acid fibers were obtained with electrospinning, then polypyrrole nanoparticles (PPy NPs) were coated onto the porous fibers with oxidation polymerization to prepare electrically conductive fibers with about 1.24 µm of diameter, and their surface conductivity was about 50 mS. The results of L929 cell test showed that more than 55% of cells grew along the aligned porous fiber axis, confirming that the cell guidance of aligned porous fibers was better than that of non-porous fibers. The results of differentiated PC12 cells on porous fibers showed that the alignment degree of neurite outgrowth and average neurite length of the cells were 84% and 111 µm, respectively, which were larger than those on the non-porous fibers. A primary mechanism was proposed to explain effect of these pores on cell/neurite adhesion and orientation along the aligned porous fibers.