Unobstructive Heartbeat Monitoring of Sleeping Infants and Young Children Using Sheet-Type PVDF Sensors.

Techniques for noninvasively acquiring the vital information of infants and young children are considered very useful in the fields of healthcare and medical care. An unobstructive measurement method for sleeping infants and young children under the age of 6 years using a sheet-type vital sensor with a polyvinylidene fluoride (PVDF) pressure-sensitive layer is demonstrated. The signal filter conditions to obtain the ballistocardiogram (BCG) and phonocardiogram (PCG) are discussed from the waveform data of infants and young children. The difference in signal processing conditions was caused by the physique of the infants and young children. The peak-to-peak interval (PPI) extracted from the BCG or PCG during sleep showed an extremely high correlation with the R-to-R interval (RRI) extracted from the electrocardiogram (ECG). The vital changes until awakening in infants monitored using a sheet sensor were also investigated. In infants under one year of age that awakened spontaneously, the distinctive vital changes during awakening were observed. Understanding the changes in the heartbeat and respiration signs of infants and young children during sleep is essential for improving the accuracy of abnormality detection by unobstructive sensors.

Printed Directional Bending Sensor with High Sensitivity and Low Hysteresis for Human Motion Detection and Soft Robotic Perception.

We present a high-performance flexible bending strain sensor for directional motion detection of human hands and soft robotic grippers. The sensor was fabricated using a printable porous conductive composite composed of polydimethylsiloxane (PDMS) and carbon black (CB). The utilization of a deep eutectic solvent (DES) in the ink formulation induced a phase segregation between the CB and PDMS and led to a porous structure inside the printed films after being vapored. This simple and spontaneously formed conductive architecture provided superior directional bend-sensing characteristics compared to conventional random composites. The resulting flexible bending sensors displayed high bidirectional sensitivity (gauge factor of 45.6 under compressive bending and 35.2 under tensile bending), negligible hysteresis, good linearity (>0.99), and excellent bending durability (over 10,000 cycles). The multifunctional applications of these sensors, including human motion detection, object-shape monitoring, and robotic perceptions, are demonstrated as a proof-of-concept.

Layout-to-Bitmap Conversion and Design Rules for Inkjet-Printed Large-Scale Integrated Circuits.

Digital inkjet printing (IJP) can greatly reduce the manufacturing cost and waste of flexible large-area electronics by adding micro-fine patterns onto plastic foils. Advanced system design using IJP has been limited by the lack of an electronic design automation (EDA) approach. An EDA approach based on a vector-based layout drawing requires parameterized IJP design rules. This study proposes a layout-to-bitmap (L2B) conversion procedure and line-based design rules that leverage the existing circuit layout EDA tools for advanced IJP designs. The L2B conversion is accomplished by optimizing the parameters of the horizontal and vertical lines by varying the drop spacings and platen temperatures. Next, the line-based layouts are converted to bitmap files which are used as IJP input data for printing multiple metal layers. This study systematically investigated the development of an IJP process employing Ag nanoparticles. The physical characteristics of the proposed process were evaluated based on theories concerning inkjet-printed bead formation. The design rules for fabricating printed thin-film transistor (TFT) circuits were documented. Documentation is the first step in creating an IJP process design kit for advanced electronics design. Using the optimized L2B conversion procedure and the design rules, a 10 × 10 array of printed organic TFTs was fabricated to demonstrate the reliability of the developed process. Additionally, the fabricated printed organic TFTs indicated that the proposed process could be extended to large-scale system designs.

A fully screen-printed potentiometric chloride ion sensor employing a hydrogel-based touchpad for simple and non-invasive daily electrolyte analysis.

This is the first report demonstrating proof of concept for the passive, non-invasive extraction and in situ potentiometric detection of human sweat chloride ions (Cl- ions) using a stable printed planar liquid-junction reference electrode-integrated hydrogel-based touch-sensor pad without activities such as exercise to induce perspiration, environmental temperature control, or requiring cholinergic drug administration. The sensor pad was composed entirely of a screen-printed bare Ag/AgCl-based chloride ion-selective electrode and a planar liquid-junction Ag/AgCl reference electrode, which were fully covered by an agarose hydrogel in phosphate-buffered saline (PBS). When human skin contacted the hydrogel pad, sweat Cl- ions were continuously extracted into the gel, followed by in situ potentiometric detection. The planar liquid-junction Ag/AgCl reference electrode had a polymer-based KCl-saturated inner electrolyte layer to stabilize the potential of the Ag/AgCl electrode even with a substantial change in the chloride ion concentration in the hydrogel pad. We expect this fully screen-printed sensor to achieve the low-cost passive and non-invasive daily monitoring of human Cl- ions in sweat in the future.

Low Bandgap Bistetracene-Based Organic Semiconductors Exhibiting Air Stability, High Aromaticity and Mobility.

The benchmark of soluble organic semiconductors based on acenes is the 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-PEN). However TIPS-PEN still suffers from photoinduced oxidation due to its low degree of aromaticity. Increasing the aromaticity while keeping similar optical and electrochemical properties as well as a shape suitable for good hole transport can be achieved with two-dimensional polycyclic aromatic hydrocarbons (2D-PAHs). Herein, we present an efficient synthesis and characterization of bistetracene derivatives that exhibit a band gap up to 1.71 eV and an increased stability up to 21 times compared to TIPS-PEN and mobility over 0.1 cm2 V-1 s-1 in solution-processed organic field-effect transistors. Based on simple structural consideration, the high stability is attributed to the aromaticity of the bistetracene which is comparable to an anthrancene along each tetracene. According to Clar's sextet rule, the bistetracene should be best regarded as two anthracenes fused at the face bridged by two ethylenic spacers. The synthesis path paves the way towards the preparation of ambipolar and/or longer 2D-PAHs such as bispentacenes and could give rise to organic semiconductors with interesting properties.

Antibody- and Label-Free Phosphoprotein Sensor Device Based on an Organic Transistor.

An antibody- and label-free detection of a phosphoprotein (α-casein) has been achieved using an organic field-effect transistor (OFET)-based sensor. The fabricated OFET device possesses an extended-gate electrode functionalized with an artificial phosphoprotein receptor (Zn(II)-dipicolylamine complex, Zn(II)-DPA). It is shown that the OFET responds to the molecular recognition processes involving the Zn(II)-DPA at the extended-gate electrode. The binding of α-casein to the receptor in a HEPES solution results in an analyte-specific changes of the drain current of the OFET. The successful demonstration of the antibody- and label-free detection using the OFET could pave the way to the development of low-cost, disposable, and portable electronic sensor devices.

Label-Free Detection of Human Glycoprotein (CgA) Using an Extended-Gated Organic Transistor-Based Immunosensor.

Herein, we report on the fabrication of an extended-gated organic field-effect transistor (OFET)-based immunosensor and its application in the detection of human chromogranin A (hCgA). The fabricated OFET device possesses an extended-gate electrode immobilized with an anti-CgA antibody. The titration results of hCgA showed that the electrical changes in the OFET characteristics corresponded to the glycoprotein recognition ability of the monoclonal antibody (anti-CgA). The observed sensitivity (detection limit: 0.11 µg/mL) and selectivity indicate that the OFET-based immunosensor can be potentially applied to the rapid detection of the glycoprotein concentration without any labeling.

Enhanced adhesion mechanisms between printed nano-silver electrodes and underlying polymer layers.

We have characterized mechanisms to improve the adhesion between printed electrodes prepared from silver nanoparticle inks and underlying polymer layers. Adhesion strength was significantly improved by sintering the inks above the glass transition temperature of the polymer underlayers, whereby enhanced adhesion was realized through interfacial fusion between the silver electrode layer and the underlying polymer layer. The surface energy of the underlayer was found to be an important factor in the improvement of adhesive strength, in that larger and thicker interfused regions between layers were observed for underlayers that had higher surface energies.

Benzimidazole derivatives: synthesis, physical properties, and n-type semiconducting properties.

A series of new benzimidazole derivatives were synthesized by the solid-state condensation and direct sublimation (SSC-DS) method and their physical properties were investigated. The reaction yields and product stability were significantly affected by the identity of the diamine and anhydride substituents. On the other hand, the substituents of the benzimidazole ring allowed fine tuning of the emission maxima, fluorescence quantum yields, and redox potentials. The HOMO-LUMO levels were estimated by cyclic voltammetry in film on indium tin oxide (ITO) and compared with values obtained by other methods. The described benzimidazoles showed high crystallinity, which is attributed to a high planarity and interactions between carbon and heteroatoms. These compounds showed n-type semiconducting behavior in organic field-effect transistors (OFETs). Optimized devices for fluorinated NTCBI (naphthalene tetracarboxylic bisbenzimidazole) showed respectable electron mobilities of ∼10(-2)  cm(2) V(-1) s(-1) .

Dual-gate thin film transistor lactate sensors operating in the subthreshold regime.

Organic thin-film transistors (TFTs) with an electrochemically functionalized sensing gate are promising platforms for wearable health-monitoring technologies because they are light, flexible, and cheap. Achieving both high sensitivity and low power is highly demanding for portable or wearable devices. In this work, we present flexible printed dual-gate (DG) organic TFTs operating in the subthreshold regime with ultralow power and high sensitivity. The subthreshold operation of the gate-modulated TFT-based sensors not only increases the sensitivity but also reduces the power consumption. The DG configuration has deeper depletion and stronger accumulation, thereby further making the subthreshold slope sharper. We integrate an enzymatic lactate-sensing extended-gate electrode into the printed DG TFT and achieve exceptionally high sensitivity (0.77) and ultralow static power consumption (10 nW). Our sensors are successfully demonstrated in physiological lactate monitoring with human saliva. The accuracy of the DG TFT sensing system is as good as that of a high-cost conventional assay. The developed platform can be readily extended to various materials and technologies for high performance wearable sensing applications.

Printed Composite Film with Microporous/Micropyramid Hybrid Conductive Architecture for Multifunctional Flexible Force Sensors.

Porous structures and micropatterning surfaces play a crucial role in the development of highly sensitive force sensors. However, achieving these two conductive architectures typically requires the synthesis of complex materials and expensive manufacturing processes. In this study, we introduce a novel conductive composite film featuring a microporous/micropyramid hybrid conductive architecture, which is achieved through a straightforward process of materials mixing and one-step screen printing. By utilizing a deep eutectic solvent in the ink component, micropores are induced in the printed composite, while the mesh of the screen mask acts as a template, resulting in a micropyramid film surface. We have successfully realized highly sensitive flexible force sensors (0.15 kPa-1) with multifunctional capabilities for perceiving normal force and shear force.

Development of a highly sensitive Prussian-blue-based enzymatic biosensor for L-carnitine employing the thiol/disulfide exchange reaction.

This is the first report of conducting proof-of-concept study for amperometric acetyltransferase-based L-carnitine sensor by employing the thiol/disulfide exchange reaction. The carnitine acetyltransferase (CrAT) catalyzes the reaction between acetyl-CoA and L-carnitine to produce CoA which is difficult to detect directly by electrochemical methods owing to steric hindrance and electrostatic effect of CoA. The thiol/disulfide exchange reaction between CoA and cystamine was mediated in the enzymatic reaction to produce electrochemically detectable low molecular weight of cationic cysteamine. The sensor exhibited high sensitivity and selectivity for L-carnitine in the concentration range 0.28-50 µM with a limit of detection of 0.28 µM. This is a promising strategy for L-carnitine sensing in point-of-care testing applications.

N-Type Printed Organic Source-Gated Transistors with High Intrinsic Gain.

Source-gated transistors (SGTs) are emerging devices enabling high-gain single-stage amplifiers with low complexity. To date, the p-type printed organic SGT (OSGT) has been developed and showed high gain and low power consumption. However, complementary OSGT circuits remained impossible because of the lack of n-type OSGTs. Here, we show the first n-type OSGTs, which are printed and have a high intrinsic gain over 40. A Schottky source contact is intentionally formed between an n-type organic semiconductor, poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (N2200), and the silver electrode. In addition, a blocking layer at the edge of the source electrode plays an important role to improve the saturation characteristics and increase the intrinsic gain. Such n-type printed OSGTs and complementary circuits based on them are promising for flexible and wearable electronic devices such as for physiological and biochemical health monitoring.

A Printed Flexible Humidity Sensor with High Sensitivity and Fast Response Using a Cellulose Nanofiber/Carbon Black Composite.

In the emerging Internet of Things (IoT) society, there is a significant need for low-cost, high-performance flexible humidity sensors in wearable devices. However, commercially available humidity sensors lack flexibility or require expensive and complex fabrication methods, limiting their application and widespread use. We report a high-performance printed flexible humidity sensor using a cellulose nanofiber/carbon black (CNF/CB) composite. The cellulose nanofiber enables excellent dispersion of carbon black, which facilitates the ink preparation and printing process. At the same time, its hydrophilic and porous nature provides high sensitivity and fast response to humidity. Significant resistance changes of 120% were observed in the sensor at humidity ranging from 30% RH to 90% RH, with a fast response time of 10 s and a recovery time of 6 s. Furthermore, the developed sensor also exhibited high-performance uniformity, response stability, and flexibility. A simple humidity detection device was fabricated and successfully applied to monitor human respiration and noncontact fingertip moisture as a proof-of-concept.

A heat-melt adhesive-assisted transferable electrode films.

This report is the first on heat-assisted transferable battery components, enabling manufacturing batteries on non-planer surfaces such as a curved surface and an edge. The transferrable battery components were composed of two layers: a cathode or an anode and a conductive heal-melt adhesive layer on a silicone-based flexible supporting paper. These mechanically-durable, flexible components enabled conformable adhesion even on curved surfaces and substrate edges. As a model battery, the manganese dioxide-zinc system was constructed on a curved surface using transfer techniques and showed a practical capacity of 1.8 mAh cm-2 per unit electrode area. These transferable electrodes allow arbitrary design of batteries according to the power consumption of IoT devices to be fabricated on unreported geometries where has been considered as a dead space.

Control of Molecular Orientation in Organic Semiconductors Using Weak Iodine-Iodine Interactions.

Controlling the molecular orientation of materials is a key issue for improving the performance of organic semiconductor devices. Herein, we demonstrate the structure-property relationships of iodinated and noniodinated molecules based on an asymmetric thienoacene framework. The noniodinated molecule formed an antiparallel slip-stack structure with small orbital overlap between molecules. In contrast, the iodinated molecule formed a head-to-head layered-herringbone structure, and as a result, the transfer integrals became larger and the hole mobility increased significantly compared with the noniodinated material. The iodinated molecule was made into a stable and solution-processable p-type organic semiconductor with a mobility of 2.2 cm2 V-1 s-1, which was 2 orders of magnitude higher than that of the noniodinated molecule. This study reveals that controlling molecular orientations using iodine-iodine interactions is a promising strategy for accelerating the development of organic semiconductor materials.

Constructive Optimization of a Multienzymatic Film Based on a Cascade Reaction for Electrochemical Biosensors.

The application of a multienzyme cascade reaction in electrochemical biosensors has the advantage of expanding the target substrates in addition to selectivity combining multiple enzymes on an electrode. However, the multienzyme system has the drawback of inefficient substance conversion because of the time-consuming passing of intermediates between the enzymes and/or diffusional loss of the intermediates. In this study, the optimal construction of a multienzymatic film in an ammonia detection sensor was investigated using a cascade reaction of l-glutamate oxidase and l-glutamate dehydrogenase as a model sensor. Three enzymatic films were prepared: (1) a mixed film designed to have a short diffusional distance between closely located enzymes, (2) a normal-sequential layered film arranged for the correct reaction pathway, and (3) a reverse-sequential layered film as a negative control. This was followed by comparison of the conversion efficiency of ammonia to hydrogen peroxide using time-dependent potentiometric measurements of a Prussian blue electrode determining the hydrogen peroxide amount. The results indicate that the conversion efficiency of the normal-sequential layered film was the highest among the three enzymatic films. The quantitative evaluation of the intermediate conversion efficiency of the cascade reaction showed that compared to the mixed film (34%), a higher conversion efficiency of 92% was obtained in the first enzymatic reaction step. These findings will promote the use of multienzymatic cascade reaction systems not only in biosensors and bioreactors but also in various industrial fields.

A Flexible 3D Organic Preamplifier for a Lactate Sensor.

Organic transistors are promising platforms for wearable biosensors. However, the strategies to improve signal amplification have yet to be determined, particularly regarding biosensors that generate very weak signals. In this study, an organic voltage amplifier is presented for a lactate sensor on flexible plastic foil. The preamplifier is based on a 3D complementary inverter, which is achieved by vertically stacking complementary transistors with a shared gate between them. The shared gate is extended and functionalized with a lactate oxidase enzyme to detect lactate. The sensing device successfully detects the lactate concentration in the human sweat range (20-60 mm) with high sensitivity (6.82 mV mm-1 ) due to high gain of its amplification. The 3D integration process is cost-effective as it is solution-processable and doubles the number of transistors per unit area. The device presented in this study would pave the way for the development of high-gain noninvasive sweat lactate sensors that can be wearable.

Printed Organic Transistor-based Biosensors for Non-invasive Sweat Analysis.

This review describes recent advances in biosensors for non-invasive human healthcare applications, especially focusing on sweat analysis, along with approaches for fabricating these biosensors based on printed electronics technology. Human sweat contains various kinds of biomarkers. The relationship between a trace amount of sweat biomarkers partially partitioned from blood and diseases has been investigated by omic analysis. Recent progress in wearable or portable biosensors has enabled periodic or continuous monitoring of some sweat biomarkers while supporting the results of the omic analysis. In this review, we particularly focused on a transistor-based biosensor that is highly sensitive in quantitatively detecting the low level of sweat biomarkers. Furthermore, we showed a new approach of flexible hybrid electronics that has been applied to advanced sweat biosensors to realize fully integrated biosensing systems wirelessly connected to a networked IoT system. These technologies are based on uniquely advanced printing techniques that will facilitate mass fabrication of high-performance biosensors at low cost for future smart healthcare.

Fully Printed PEDOT:PSS-based Temperature Sensor with High Humidity Stability for Wireless Healthcare Monitoring.

Facile fabrication and high ambient stability are strongly desired for the practical application of temperautre sensor in real-time wearable healthcare. Herein, a fully printed flexible temperature sensor based on cross-linked poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) was developed. By introducing the crosslinker of (3-glycidyloxypropyl)trimethoxysilane (GOPS) and the fluorinated polymer passivation (CYTOP), significant enhancements in humidity stability and temperature sensitivity of PEDOT:PSS based film were achieved. The prepared sensor exhibited excellent stability in environmental humidity ranged from 30% RH to 80% RH, and high sensitivity of -0.77% °C-1 for temperature sensing between 25 °C and 50 °C. Moreover, a wireless temperature sensing platform was obtained by integrating the printed sensor to a printed flexible hybrid circuit, which performed a stable real-time healthcare monitoring.