甚野 裕明

Next-generation biomedical devices(1-9) will need to be self-powered and conformable to human skin or other tissue. Such devices would enable the accurate and continuous detection of physiological signals without the need for an external power supply or bulky connecting wires. Self-powering functionality could be provided by flexible photovoltaics that can adhere to moveable and complex three-dimensional biological tissues(1-4) and skin(5-9). Ultra-flexible organic power sources(10-13) that can be wrapped around an object have proven mechanical and thermal stability in long-term operation(13), making them potentially useful in human-compatible electronics. However, the integration of these power sources with functional electric devices including sensors has not yet been demonstrated because of their unstable output power under mechanical deformation and angular change. Also, it will be necessary to minimize high-temperature and energy-intensive processes(10,12) when fabricating an integrated power source and sensor, because such processes can damage the active material of the functional device and deform the few-micrometre-thick polymeric substrates. Here we realize self-powered ultra-flexible electronic devices that can measure biometric signals with very high signal-to-noise ratios when applied to skin or other tissue. We integrated organic electrochemical transistors used as sensors with organic photovoltaic power sources on a one-micrometre-thick ultra-flexible substrate. A high-throughput room-temperature moulding process was used to form nano-grating morphologies (with a periodicity of 760 nanometres) on the charge transporting layers. This substantially increased the efficiency of the organophotovoltaics, giving a high power-conversion efficiency that reached 10.5 per cent and resulted in a high power-per-weight value of 11.46 watts per gram. The organic electrochemical transistors exhibited a transconductance of 0.8 millisiemens and fast responsivity above one kilohertz under physiological conditions, which resulted in a maximum signal-to-noise ratio of 40.02 decibels for cardiac signal detection. Our findings offer a general platform for next-generation self-powered electronics.

Flexible organic optoelectronic devices simultaneously targeting mechanical conformability and fast responsivity in the near-infrared (IR) region are a prerequisite to expand the capabilities of practical optical science and engineering for on-skin optoelectronic applications. Here, an ultraflexible near-IR responsive skin-conformal photoplethysmogram sensor based on a bulk heterojunction photovoltaic active layer containing regioregular polyindacenodithiophene-pyridyl[2,1,3]thiadiazole-cyclopentadithiophene (PIPCP) is reported. The ultrathin (3 mu m thick) photodetector exhibits unprecedented operational stability under severe mechanical deformation at a bending radius of less than 3 mu m, even after more than 10(3) bending cycles. Deliberate optimization of the physical dimensions of the active layer used in the device enables precise on/off switching and high device yield simultaneously. The response frequency over 1 kHz under mechanically deformed conditions facilitates conformal electronic sensors at the machine/human interface. Finally, a mechanically stretchable, flexible, and skin-conformal photoplethysmogram (PPG) device with higher sensitivity than those of rigid devices is demonstrated, through conformal adherence to the flexuous surface of a fingerprint.

In this paper, the amplification of the photocurrent in organic phototransistors (OPTs) employing bulk heterojunctions (BHJs) with different donor-acceptor ratios has been studied. As a model system, poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-p-phenylene vinylene] (OC1C10-PPV) and [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM) are used as donor and acceptor, respectively, combined with Al contact. It is found that for OPTs the mobility of the majority carrier is the dominating factor for maximizing the photocurrent. This is different from organic photodiodes (OPDs) where balanced hole and electron mobilities are important. For OPDs using the same model system, the maximum photocurrent is obtained for a PCBM content of 80wt.% while for OPTs, it retained its photocurrent from PCBM 80wt.% up to PCBM 100wt.%. In addition, BHJ transistors respond more rapidly to changes in the illumination intensity than transistors with a pure PCBM layer.

Flexible photovoltaics with extreme mechanical compliance present appealing possibilities to power Internet of Things (IoT) sensors and wearable electronic devices. Although improvement in thermal stability is essential, simultaneous achievement of high power conversion efficiency (PCE) and thermal stability in flexible organic photovoltaics (OPVs) remains challenging due to the difficulties in maintaining an optimal microstructure of the active layer under thermal stress. The insufficient thermal capability of a plastic substrate and the environmental influences cannot be fully expelled by ultrathin barrier coatings. Here, we have successfully fabricated ultraflexible OPVs with initial efficiencies of up to 10% that can endure temperatures of over 100 degrees C, maintaining 80% of the initial efficiency under accelerated testing conditions for over 500 hours in air. Particularly, we introduce a low-bandgap poly(benzodithiophene-cothieno[3,4-b] thiophene) (PBDTTT) donor polymer that forms a sturdy microstructure when blended with a fullerene acceptor. We demonstrate a feasible way to adhere ultraflexible OPVs onto textiles through a hot-melt process without causing severe performance degradation.

Flexible, transparent electrodes are a crucial component for future implantable and wearable systems. For practical applications, conductivity and flexibility should be further improved to prevent signal attenuation, heat generation, and disconnection. Herein, we fabricate an ultraflexible transparent electrode with low sheet resistance (8.6 Omega/sq) using an indium-tin-oxide/Au/indium-tin-oxide (ITO) multilayer on a 1 mu m thick parylene substrate. The electrodes were foldable and when compared to pristine ITO displayed greater mechanical robustness. Applicability for large-area applications was confirmed through electrochemical impedance measurements, and the compatibility of electrode arrays for vivo applications was demonstrated with an optogenetic experiment. As a result of the ultraflexible transparent electrode's excellent conformity to soft tissue, voltage signals induced by light stimulation directly below the electrode were successfully recorded on the moving muscle.

Thin-film electronics intimately laminated onto the skin imperceptibly equip the human body with electronic components for health-monitoring and information technologies. When electronic devices are worn, the mechanical flexibility and/or stretchability of thin-film devices helps to minimize the stress and discomfort associated with wear because of their conformability and softness. For industrial applications, it is important to fabricate wearable devices using processing methods that maximize throughput and minimize cost. We demonstrate ultraflexible and conformable three-color, highly efficient polymer light-emitting diodes (PLEDs) and organic photodetectors (OPDs) to realize optoelectronic skins (oe-skins) that introduce multiple electronic functionalities such as sensing and displays on the surface of human skin. The total thickness of the devices, including the substrate and encapsulation layer, is only 3 mu m, which is one order of magnitude thinner than the epidermal layer of human skin. By integrating green and red PLEDs with OPDs, we fabricate an ultraflexible reflective pulse oximeter. The device unobtrusively measures the oxygen concentration of blood when laminated on a finger. On-skin seven-segment digital displays and color indicators can visualize data directly on the body.

The development of advanced flexible large-area electronics such as flexible displays and sensors will thrive on engineered functional ink formulations for printed electronics where the spontaneous arrangement of molecules aids the printing processes. Here we report a printable elastic conductor with a high initial conductivity of 738 S cm (-1) and a record high conductivity of 182 S cm(-1) when stretched to 215% strain. The elastic conductor ink is comprised of Ag flakes, a fluorine rubber and a fluorine surfactant. The fluorine surfactant constitutes a key component which directs the formation of surface-localized conductive networks in the printed elastic conductor, leading to a high conductivity and stretchability. We demonstrate the feasibility of our inks by fabricating a stretchable organic transistor active matrix on a rubbery stretchability-gradient substrate with unimpaired functionality when stretched to 110%, and a wearable electromyogram sensor printed onto a textile garment.