Stretchable, Skin-Attachable Electronics with Integrated Energy Storage Devices for Biosignal Monitoring.

The demand for novel electronics that can monitor human health, for example, the physical conditions of individuals, during daily life using different techniques from those used in traditional clinic diagnostic facilities is increasing. These novel electronics include stretchable sensor devices that allow various biosignals to be directly measured on human skin without restricting routine activity. The thin, skin-like characteristics of these devices enable stable operation under various deformations, such as stretching, pressing, and rubbing, experienced while attached to skin. The mechanically engineered design of these devices also minimizes the inconvenience caused by long-term wear owing to conformal lamination on the skin. The final form of a skin-attachable device must be an integrated platform with an independent and complete system containing all components on a single, thin, lightweight, stretchable substrate. To fabricate fully integrated devices, various aspects, such as material design for deformable interconnection, fabrication of high-performance active devices, miniaturization, and dense arrangement of component devices, should be considered. In particular, a power supply system is critical and must be combined in an electromechanically stable and efficient manner with all devices, including sensors. Additionally, the biosignals obtained by these sensors should be wirelessly transmitted to external electronic devices for free daily activity. This Account covers recent progress in developing fully integrated, stretchable, skin-attachable devices by presenting our strategies to achieve this goal. First, we introduce several integration methods used in this field to build stretchable systems with a special focus on the utilization of liquid gallium alloy. The unique characteristics and patterning process of liquid metal are summarized. Second, various skin-attachable sensors, including strain, pressure, with enhanced sensitivity and mechanical properties are discussed along with their applications for biosignal monitoring. Dual mode sensors that simultaneously detect temperature and pressure signals without interference are also introduced. Third, we emphasize supercapacitors as promising, efficient energy storage devices for power management systems in wearable devices. Supercapacitors for skin-attachable applications should have a high performance, such as high operation voltage, high energy and power densities, cyclic and air stability and water resistance. For this, strategies to select novel materials for electrode, electrolyte, and encapsulation are suggested. Several approaches to fabricate stretchable supercapacitor systems are also presented. Finally, we introduce recent examples of skin-attachable, stretchable electronics that integrate sensors, power management devices, and wireless data transfer functions on a single elastomer substrate. Conventional wireless technologies, such as near-field communications (NFC) and Bluetooth, are incorporated in miniaturized features on the devices. To date, much research has been performed in this field, but there are still many technologies to develop. The performance of individual devices and mass fabrication techniques should be enhanced. We expect that future electronic devices with fully integrated functions will include advanced human-machine interaction capabilities and expand the overall abilities of the human body.

A Flexible Loudspeaker Using the Movement of Liquid Metal Induced by Electrochemically Controlled Interfacial Tension.

A flexible liquid metal loudspeaker (LML) is demonstrated consisting of a gallium-based eutectic liquid metal (Galinstan) and basic aqueous electrolyte (NaOH(aq) ). The LML is driven by liquid metal motion induced by the electrochemically controlled interfacial tension of the Galinstan in NaOH(aq) electrolyte under an applied alternating current (AC) voltage. The fabricated LML produces sound waves in the human audible frequency band with a sound pressure level of ≈40-50 dB at 1 cm from the device and exhibits mechanical stability under bending deformation with a bending radius of 3 mm. Various sounds can be generated with the LML from a single tone to piano notes and human voices. To understand the underlying mechanism of sound generation by the LML, motion analyses, sound measurements, and electrical characterization are conducted at various frequencies. For the first time, this work suggests a new type of liquid metal-based electrochemically driven sound generator in the field of flexible acoustic devices that can be applied to future wearable electronics.

Super-Absorbent Polymer Valves and Colorimetric Chemistries for Time-Sequenced Discrete Sampling and Chloride Analysis of Sweat via Skin-Mounted Soft Microfluidics.

This paper introduces super absorbent polymer valves and colorimetric sensing reagents as enabling components of soft, skin-mounted microfluidic devices designed to capture, store, and chemically analyze sweat released from eccrine glands. The valving technology enables robust means for guiding the flow of sweat from an inlet location into a collection of isolated reservoirs, in a well-defined sequence. Analysis in these reservoirs involves a color responsive indicator of chloride concentration with a formulation tailored to offer stable operation with sensitivity optimized for the relevant physiological range. Evaluations on human subjects with comparisons against ex situ analysis illustrate the practical utility of these advances.

Topcoat-Assisted Perpendicular and Straightly Parallel Coexisting Orientations of Block Copolymer Films.

Highly ordered perpendicular orientation and straightly parallel orientation coexisting polystyrene-block-polydimethylsiloxane (PS-b-PDMS) cylindrical microdomains with 10 nm width can be realized by using polyvinyl acetate as a partially dewetted topcoat and solvent annealing with acetone vapor. During solvent annealing, the swelled topcoat begins to dewet and the dewetting rim sweeps the surface of the block copolymer films to align the cylindrical microdomains with the direction of dewetting propagation. However, the wetted region of the topcoat/PS-b-PDMS film forms with a perpendicular orientation due to reduced surface tension and sufficient concentration gradient in the solvent evaporation step. The orientational changes (perpendicular/straightly parallel orientation) in the dewetted/wetted area are also investigated according to the vapor pressure of solvent annealing. The degree of directionality of the swept PS-b-PDMS films according to the distance from the dewetting front, which is equivalent with time after sweeping, is examined. To control the direction of dewetting and complex structures within a specific area, an imprinting process is introduced to form topographical line-space patterns in the topcoat and perpendicular/parallel orientation of BCP patterns in the line-space patterns, respectively.

p-n homo-junction arrays of aligned single walled carbon nanotubes fabricated by selective patterning of polyethyleneimine film.

We describe the fabrication and electrical performance of p-n homo-junction diode arrays of horizontally aligned single walled carbon nanotubes (SWCNTs). Horizontally aligned SWCNTs grown on stable temperature-cut quartz with a density of ∼ 6 SWCNTs µm(-1) were transferred onto a SiO(2)/Si substrate. After the electrical breakdown, aligned SWCNT field effect transistors (FETs) showed unipolar p-type characteristics with a large current on/off ratio of 10(6) at 1 V and a hole mobility per tube of 1500 cm(2) V(-1) s(-1). Spin-coating of polyethyleneimine (PEI) onto p-type SWCNT FETs showed the n-type transfer characteristics. Patterning of spin-coated PEI film enabled the fabrication of p-n homo-junction arrays of aligned SWCNTs in an easy way, where the rectifying behavior was observed with a rectification ratio of ∼ 10(4) at ± 2 V. A comparative study with a p-n homo-junction of random networks of SWCNTs confirmed the advantage of aligned SWCNTs for applications in high performance electronic devices.

Body-Attachable and Stretchable Multisensors Integrated with Wirelessly Rechargeable Energy Storage Devices.

A stretchable multisensor system is successfully demonstrated with an integrated energy-storage device, an array of microsupercapacitors that can be repeatedly charged via a wireless radio-frequency power receiver on the same stretchable polymer substrate. The integrated devices are interconnected by a liquid-metal interconnection and operate stably without noticeable performance degradation under strain due to the skin attachment, and a uniaxial strain up to 50%.

Stretchable Array of Highly Sensitive Pressure Sensors Consisting of Polyaniline Nanofibers and Au-Coated Polydimethylsiloxane Micropillars.

We report on the facile fabrication of a stretchable array of highly sensitive pressure sensors. The proposed pressure sensor consists of the top layer of Au-deposited polydimethylsiloxane (PDMS) micropillars and the bottom layer of conductive polyaniline nanofibers on a polyethylene terephthalate substrate. The sensors are operated by the changes in contact resistance between Au-coated micropillars and polyaniline according to the varying pressure. The fabricated pressure sensor exhibits a sensitivity of 2.0 kPa(-1) in the pressure range below 0.22 kPa, a low detection limit of 15 Pa, a fast response time of 50 ms, and high stability over 10000 cycles of pressure loading/unloading with a low operating voltage of 1.0 V. The sensor is also capable of noninvasively detecting human-pulse waveforms from carotid and radial artery. A 5 × 5 array of the pressure sensors on the deformable substrate, which consists of PDMS islands for sensors and the mixed thin film of PDMS and Ecoflex with embedded liquid metal interconnections, shows stable sensing of pressure under biaxial stretching by 15%. The strain distribution obtained by the finite element method confirms that the maximum strain applied to the pressure sensor in the strain-suppressed region is less than 0.04% under a 15% biaxial strain of the unit module. This work demonstrates the potential application of our proposed stretchable pressure sensor array for wearable and artificial electronic skin devices.

High-density, stretchable, all-solid-state microsupercapacitor arrays.

We report on the successful fabrication of stretchable microsupercapacitor (MSC) arrays on a deformable polymer substrate that exhibits high electrochemical performance even under mechanical deformation such as bending, twisting, and uniaxial strain of up to 40%. We designed the deformable substrate to minimize the strain on MSCs by adopting a heterogeneous structure consisting of stiff PDMS islands (on which MSCs are attached) and a soft thin film (mixture of Ecoflex and PDMS) between neighboring PDMS islands. Finite element method analysis of strain distribution showed that an almost negligible strain of 0.47% existed on the PDMS islands but a concentrated strain of 107% was present on the soft thin film area under a uniaxial strain of 40%. The use of an embedded interconnection of the liquid metal Galinstan helped simplify the fabrication and provided mechanical stability under deformation. Furthermore, double-sided integration of MSCs increased the capacitance to twice that of MSCs on a conventional planar deformable substrate. In this study, planar-type MSCs with layer-by-layer assembled hybrid thin film electrodes of MWNT/Mn3O4 and PVA-H3PO4 electrolyte were fabricated; when they are integrated into a circuit, these MSCs increase the output voltage beyond the potential of the electrolyte used. Therefore, various LEDs that require high voltages can be operated under a high uniaxial strain of 40% without any decrease in their brightness. The results obtained in this study demonstrate the high potential of our stretchable MSC arrays for their application as embedded stretchable energy storage devices in bioimplantable and future wearable nanoelectronics.