Recent advances in flexible sensors for wearable and implantable devices

Flexible devices are emerging as important applications for future display, robotics, in vitro diagnostics, advanced therapies, and energy harvesting. In this review, we provide an overview of recent achievements in flexible mechanical and electrical sensing devices, focusing on the properties and functions of polymeric layers. In the order of historical development, sensing platforms are classified into four types: electronic skins for robotics and medical applications, wearable devices for in vitro diagnostics, implantable devices for human organs or tissues for surgical applications, and advanced sensing devices with additional features such as transparency, self‐power, and self‐healing. In all of these examples, a polymer layer is used as a versatile component including a flexible structural support and a functional material to generate, transmit, and process mechanical and electrical inputs in various ways. We briefly discuss some outlooks and future challenges toward the next steps for flexible devices. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1429–1441, 2013     

Preparation of multifunctional self-healing MXene/PVA double network hydrogel wearable strain sensor for monitoring human body and organ movement

In this work, a kind of conductive, self-healing hydrogel was prepared. Then it is assembled into a flexible wearable sensor for human motion detection and human-computer interaction. MXene/PVA-CBA hydrogel has super mechanical properties and excellent self-healing ability (1.8 s). It is assembled into a flexible sensor with high sensitivity, which can accurately detect various movements of the human body (ranging from frowning, speaking, and coughing on the face to bending of fingers and wrists, and body movements). Furthermore, it can be used for handwriting recognition. When it is installed on the artificial limb, it can realize the function of touching the capacitive screen. It solves the problem of using silicone prostheses to control the screen and has broad research potential in the field of intelligent robots. Therefore, the flexible wearable sensor composed of MXene/PVA-CBA hydrogel has great potential in human motion detection, bionic intelligent robot, and intelligent detection.     

Cracked titanium film on an elastomeric substrate for highly flexible,transparent, and low-power strain sensors

Strain-dependent cracking behaviors in thin titanium (Ti) films on polydimethylsiloxane (PDMS) substrates were systematically investigated for their application to sensitive, flexible, transparent, and portable strain sensors. When uniaxially elongated, vertical cracks were developed in the low-strain range, and beyond a critical strain, tilted cracks appeared to intersect the vertical cracks. The cracking behaviors were also dependent on Ti film thickness. The varying strain-dependent crack patterns produced a significant resistance change in response to the applied strain, particularly, in the high- and broad-strain range. For a 180-nm-thick Ti film on PDMS substrate, a gauge factor of 2 was achieved in the range of 30% to 50% strain. The operation power was extremely low. All the Ti films on PDMS substrates were transparent, highly flexible, and very easy to fabricate. These results suggest that cracked Ti films on PDMS substrates could be a viable candidate for realizing a low-cost, flexible, transparent, and portable strain sensor.     

高弹性MXene/TPU纳米纤维纱线的制备及其应变传感性能

采用静电纺丝技术制备了热塑性聚氨酯弹性体(TPU)纳米纤维膜,并通过"Biscrolling"的方法制备高弹性过渡金属碳化物/氮化物(Ti_3C_2T_x MXene)改性TPU纳米纤维纱线。通过SEM、电阻测试、传感性能测试等对复合纳米纤维纱线进行结构和性能表征。结果显示,随着MXene负载量的增加,复合纱线的强度先增加后降低,断裂伸长率可达459%以上,展现出优异的弹性和弹性回复性;MXene片可在纳米纤维纱线表面及内部形成连续导电薄膜,赋予复合纱线较好的导电性[电阻(76±16)?/cm]。纱线的应变传感性能测试表明,MXene/TPU纳米纤维纱线的传感系数可高达477.86,线性度高达0.995,高于绝大多数文献报道的纱线传感器,并且在监测人体的各种运动状态上展现出较好的应变传感性能。     

高弹性MXene/TPU纳米纤维纱线的制备及其应变传感性能

采用静电纺丝技术制备了热塑性聚氨酯弹性体(TPU)纳米纤维膜,并通过“Biscrolling”的方法制备高弹性过渡金属碳化物/氮化物（Ti3C2Tx MXene）改性TPU纳米纤维纱线。通过SEM、电阻测试、传感性能测试等对复合纳米纤维纱线进行结构和性能表征。结果显示,随着MXene负载量增加,复合纱线的强度先增加后降低,断裂伸长率可高达459%以上,展现出优异的弹性和弹性回复性;MXene片可在纳米纤维纱线表面及内部形成连续导电薄膜,赋予复合纱线较好的导电性（电阻76 Ω/cm）。纱线的应变传感性能测定实验表明,MXene/TPU纳米纤维纱线的传感系数可高达477.86,线性度高达0.995,高于绝大多数文献报道的纱线传感器,并且可以监测人体的各种运动状态,展现出较好的应变传感性能,在智能可穿戴领域展现出广泛的应用前景。     

Fabrication of a fibrous MnO2@MXene/CNT electrode for high-performance flexible supercapacitor

As shining stars of 2-dimensional materials, transition metal carbides (MXene) and transition metal oxides have attracted much interest in various energy fields due to their excellent conductive and electrochemical properties. However, big challenge still remains in the accessibility of high-performance fibrous electrodes for flexible supercapacitors. In this paper, MnO₂ nanorods are loaded on MXene sheets to obtain MnO₂@MXene composites by a facile hydrothermal method, which are subsequently coated on carbon nanotube fibers (CNTFs). With a fine control on morphology, the resulting MnO₂@MXene/CNTF electrode exhibits a high specific capacitance of 181.8 F/g at 1 A/g, a capacitance retention of 91% after 5000 charge-discharge cycles, as well as superb flexibility, i.e., neglected capacitance loss at a bending angle of 180°. The as-fabricated flexible composite fiber opens a new door for transition metal carbides and transition metal oxides with great potential in flexible electronics.     

Flexible and high-sensitivity piezoresistive sensor based on MXene composite with wrinkle structure

Due to the portability, good flexibility and excellent sensing performance, flexible piezoresistive sensors have received great attention in the field of transient electronic skin, intelligent robots and human-machine interaction. However, achieving both high sensitivity and wide sensing range by low-cost and large-scale method still remains a key challenge for developing high performance piezoresistive sensors. Here, a flexible and highly sensitive piezoresistive sensor was designed and realized by combining the 2D MXene material with wrinkle structure. The MXene composite based sensor with wrinkle structure was fabricated by spraying the active material onto the surface of a pre-stretched polyacrylate tape, which is facile, efficient and low-cost. The MXene composite based sensor demonstrates high sensitivity (148.26 kPa⁻¹), wide pressure range (up to 16 kPa), short response time (120 ms) and excellent durability (>13000 cycles). Moreover, benefiting from the extraordinary sensing performance and flexibility, the sensor can detect human physiological signals, monitor intelligent robot postures and map spatial pressure distributions, thus exhibiting great potential in physiological analysis systems, humanoid robotics and biomedical prostheses.     

A self-healing and conductive ionic hydrogel based on polysaccharides for flexible sensors

In this study, we proposed a self-healing conductive hydrogel based on polysaccharides and Li⁺ to serve as flexible sensors. At first, the oxidized sodium alginate(OSA) was obtained through the oxidation reaction of sodium alginate(SA). Then OSA, carboxymethyl chitosan(CMC), and agarose(AGO) were dissolved in Li Cl solution, respectively. Finally, the hydrogel was obtained through heating, mixing, and cooling processes. Because of the Schiff base structure and hydrogen bonding, the hy...     

Design of piezoelectric nanogenerator based on BiFeO3/epoxy resin with potential application for wearable electronic devices

Growing demand for electric energy in newly developed electronic systems causes increasing interest in research on piezoelectric nanogenerators (PENGs). Design and fabrication of such devices is challenging, considering cost of materials used in their construction. This is the main reason why intensive research has begun on 0-3 composites with piezoelectric properties. One of the most promising constituent materials for composites fabrication are polymers, due to their low cost and easy processing. Herein, we present fabricated wearable PENG with good impact and vibration energy conversion properties. Correlation between matrix stiffness and piezoelectric properties of 0-3 type composite is proposed. It was found that composite with 10 wt.% of BiFeO₃ particles exhibits power output density for vibrations, finger tapping, and air stream pressure P = 11.12 nW cm⁻³, P = 4.83 μW cm⁻³, and P = 769.2 μW cm⁻³, respectively. Decrease in stiffness of epoxy matrix results at least in two-times lower power output density for this same PENG. The obtained results demonstrate that the fabricated BFO/epoxy composites show the wide applicability and potential to be integrated with other functional devices, for example, as a part of wearable devices in smart shoes.     

Gold nanoparticles/water-soluble carbon nanotubes/aromatic diamine polymer composite films for highly sensitive detection of cellobiose dehydrogenase gene

An electrochemical sensor based on gold nanoparticles (GNPs)/multiwalled carbon nanotubes (MWCNTs)/poly (1,5-naphthalenediamine) films modified glassy carbon electrode (GCE) was fabricated. The effectiveness of the sensor was confirmed by sensitive detection of cellobiose dehydrogenase (CDH) gene which was extracted from Phanerochaete chrysosporium using polymerase chain reaction (PCR). The monomer of 1,5-naphthalenediamine was electropolymerized on the GCE surface with abundant free amino groups which enhanced the stability of MWCNTs modified electrode. Congo red (CR)-functionalized MWCNTs possess excellent conductivity as well as high solubility in water which enabled to form the uniform and stable network nanostructures easily and created a large number of binding sites for electrodeposition of GNPs. The continuous GNPs together with MWCNTs greatly increased the surface area, conductivity and electrocatalytic activity. This electrode structure significantly improved the sensitivity of sensor and enhanced the DNA immobilization and hybridization. The thiol modified capture probes were immobilized onto the composite films-modified GCE by a direct formation of thiol–Au bond and horseradish peroxidase–streptavidin (HRP–SA) conjugates were labeled to the biotinylated detection probes through biotin–streptavidin bond. Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to investigate the film assembly and DNA hybridization processes. The amperometric current response to HRP-catalyzed reaction was linearly related to the common logarithm of the target nucleic acid concentration in the range of 1.0 × 10⁻¹⁵–1.0 × 10⁻¹⁰ M, with the detection limit of 1.2 × 10⁻¹⁶ M. In addition, the electrochemical biosensor exhibited high sensitivity, selectivity, stability and reproducibility.     

Ferrite ceramic filled poly-dimethylsiloxane composite with enhanced magnetic-dielectric properties as substrate material for flexible electronics

Improving magnetic-dielectric properties of polymer materials, through filler of functional ceramics, provides feasibility to develop high-frequency flexible electronics. Poly-dimethylsiloxane (PDMS), an inert silicone with low elasticity modulus and high transparency, has been considered a promising candidate for flexible electronics. Current PDMS matrix used in high-frequency devices suffers from unsatisfactory properties due to very low dielectric constant. In this study, using ultrasonic stirring and vacuum-pumping process, we prepare a series of xCo₂Z/PDMS (x = 2; 4; 6; 8; 10) composite films, which are consisted of PDMS matrix and different quantity of micro-sized ferrite particles. XRD pattern indicates that the obtained ferrite particles include Co₂Z main phase and BaM second phase. We demonstrate that 4Co₂Z/PDMS film has improved magnetic-dielectric properties at 800 MHz (μ' = 1.49; ε' = 4.54 tanδ_μ = 0.058; tanδ_ε = 0.008). Also, the film has high saturation magnetization (σ_s = 17.51 emu/g). Furthermore, SEM micrographs show that using ultrasonic stirring and fast curing, the micro-sized ferrite particles are well dispersed in PDMS matrix. Our study, which provides a simple method to improve high-frequency magnetic and dielectric properties of PDMS matrix, could pave the way for development of high-frequency flexible electronics.     

Fabrication of high-quality flexible transparent conductive thin films with a Nb2O5/AgNWs/Nb2O5 sandwich structure

Different sandwich structures of flexible transparent conductive thin film (TCFs) composed of Nb₂O₅ layers and Ag nanowires (AgNWs) have been prepared onto flexible polyethylene terephthalate (PET) substrate at room temperature to develop an indium-free TCF. The AgNWs are synthesized by a modified polyol method and inserted into the Nb₂O₅ layers that are prepared by radio frequency magnetron sputtering. The optical and electrical properties can be modified by changing the number of spin-coating cycle of AgNW suspension. At optimized condition, we achieve a flexible Nb₂O₅/AgNWs/Nb₂O₅ sandwich thin film with a low sheet resistance of 9.61 Ω/square and a high optical transmittance of 84.3%. Meanwhile, the resistance remains nearly constant after 30 tape tests, suggesting a strong adhesion to the PET substrate. The sandwich thin films show high long-term stability to oxidation, humid heat, and chemicals compared with that of AgNW networks, which can be attributed to the effective covering of Nb₂O₅ layer on the AgNWs. In addition, the Nb₂O₅/AgNWs/Nb₂O₅ sandwich thin films show good stability after repeated bending. This Nb₂O₅/AgNWs/Nb₂O₅ sandwich thin film can therefore serve as a high-performance transparent conductive electrode for numerous flexible electronic devices.     

Butyl pyrene containing poly(arylene ethynylene)s for highly sensitive and selective sensing of TNT

A series of poly(arylene ethynylene)s (PAEs) containing ^tbutyl pyrene in the main chain were synthesized for nitroaromatic sensors. As control, similar polymers containing unsubstituted pyrene were also synthesized. The sensory properties of the polymers were studied towards various nitroaromatic compounds like trinitrotoluene (TNT), dinitrotoluene (DNT), nitrotoluene (NT), nitrobenzene (NB) and picric acid (PA) in solution as well as vapor state. Interestingly, all the ^tbutyl substituted pyrene containing polymers showed higher sensitivity than the corresponding unsubstituted pyrene containing polymers. Moreover, the polymers showed high sensitivity towards TNT as compared to the other nitroaromatic compounds. The sensitivity of one of the polymer PB was found several folds higher than that of the similar reported polymer containing unsubstituted pyrene ring. In addition, ^tbutyl pyrene containing polymers were found to have improved molecular weight, thermal stability, fluorescence quantum yield, film forming properties and solubility in common organic solvents as compared to the control polymers.     

Development of biopolymer composite films based on chicory extract reinforced polyvinyl alcohol/chitosan blend via green approach for flexible optoelectrical devices

Biopolymer blend composite films based on polyvinyl alcohol (PVA) and chitosan (CS) incorporated with varying amounts of chicory extract (CE) have been developed by the green solution casting technique. The impact of CE content on structural, thermal, mechanical and electrical properties was thoroughly examined. The existence of intermolecular interactions in the blend composite was confirmed by Fourier-transform infrared and ultraviolet spectroscopy. The x-ray diffraction pattern proved the successful preparation of PVA/CS/CE composite film. The scanning electron microscopy images of the composites showed shape and grain size for the different bio-filler contents. The thermal transition temperature of the blend composites was significantly improved by the addition of CE extract deduced from differential scanning calorimetry. The dielectric study showed that the permittivity remarkably increases with decreasing frequency and maximum dielectric constant was observed for 15 wt% loading. The activation energy obtained from the AC conductivity decreased as the temperature increased. The addition of CE extract improved the hardness and tensile strength of the PVA/CS blend composite in comparison with a pristine pure blend. The controllable mechanical, thermal, optical, and electrical characteristics of the PVA/CS blend composite suggest that it might be an attractive optical material for the advancement of futuristic flexible-type optoelectronic and energy storage systems.     

Remotely tuned multistate resistive switching in MoS2/NiMnIn thin film heterostructure for highly flexible ReRAM application

In this article, the Cu/MoS₂/NiMnIn memory structure was fabricated over stainless steel substrate for flexible electronics applications. The bipolar resistive switching characteristics were observed in two different fabricated devices (i) without sulfur vacancies (D₁) and (ii) with sulfur vacancies (D₂) in MoS₂ thin film. Three different resistance states such as the high resistance state (HRS), intermediate resistance state (IRS) and low resistance state (LRS) have been detected for the D₂ memory device. It could be ascribed to the two filamentary models based on the movement of sulfur vacancies and the formation of Cu metallic filament with applied bias voltage. Moreover, the Ohmic and modified space charge limited conduction mechanisms clearly explain the current conduction in different resistance states of device D₂. The fabricated MoS₂ thin film-based memory structure exhibits stable resistive switching behavior with a high OFF/ON ratio of ～3.6 × 10³, good consistency of ～3600 endurance cycles and excellent data retention capability up to 3000 s. Moreover, the remote tuning of device D₂ was thoroughly investigated and an appreciable change in SET voltage was detected with external temperature and magnetic field. Additionally, the external magnetic field altered the switching states and enhanced the multi-bit data storage capability of the memory device. This can be ascribed to the effect of the Lorentz force on ionic movement in the presence of the external magnetic field. The mechanical flexibility of the memory structure was tested for 1000 bending cycles at various bending angles in both the tensile and compressive bending modes. Hence, the present study opens up new ways for the futuristic flexible device for high data storage and neuromorphic computing applications.     

Fabrication and photoelectrochemical properties of TiO2 films on Ti substrate for flexible dye-sensitized solar cells

The dye-sensitized solar cells (DSSCs) using Ti foil supporting substrate for fabricating nanocrystalline TiO₂ flexible film electrodes were developed, intending to improve the photoelectrochemical properties of flexible substrate-based DSSCs. The obtained cells were characterized by electrochemical impedance spectra (EIS), open circuit voltage decay (OCVD) measurement and Tafel plots. The experimental results indicate that the most important advantage of a Ti foil-based TiO₂ flexible electrode over a FTO glass-based electrode lies in its reduced sheet resistance, electron traps, and the retarded back reaction of electrons with tri-iodine ions in DSSCs. All above characteristics for the Ti substrate TiO₂ films are beneficial for decreasing the charge recombination in the TiO₂ electrode and prolonging the electron lifetimes for the DSSCs, as well as improvement of the overall solar conversion efficiency. The photocurrent of the cell fabricated with the Ti foil-based flexible electrode increased significantly, leading to a much higher overall solar conversion efficiency of 5.45% at 100 mW/cm² than the cell made with FTO glass-based TiO₂ electrodes. Above results demonstrate that Ti foil is a potential alternative to the conventional FTO glass substrate for the DSSCs.     

Ga and Ti co-doped In2O3 films for flexible amorphous transparent conducting oxides

We designed Ga and Ti co-doped In₂O₃ (IGTO) films to use as a flexible and transparent amorphous conducting oxide electrode in thin film heaters (TFHs) and flexible touch screen panels (FTSPs) for automobiles. The properties of the IGTO electrodes deposited on cyclic olefin copolymer (COP) at room temperature were investigated as a function of the O₂/(Ar + O₂) flow ratio, to confirm the best sputtering condition for transparent and flexible electrode. Depending on the oxygen flow ratio, the IGTO/COP electrodes showed sheet resistance of (39.3 – 1.57) × 10⁴ Ohm/sq, an average transmittance of (84.90 – 87.12) % at visible wavelength area, and a surface roughness of (0.95 – 3.23) nm. In addition, IGTO/COP samples exhibited good mechanical flexibility with critical bending radius of 3 mm, which is enough to be used as FTSPs. From the previously mentioned results, we found the amorphous IGTO/COP to be a promising flexible and transparent electrode for curved TFHs and FTSPs. The flexible IGTO/COP TFHs demonstrated a saturated temperature of 78.6 °C when applied with low operating direct current (DC) of 8 V, due to its low sheet resistance. In addition, the IGTO/COP FTSPs showed very stable touch sensitivity, even at a bent state. We found that the optimized IGTO/COP is a promising flexible and transparent electrode for next-generation automobiles.     

Flexible and sensitive piezoresistive electronic skin based on TOCN/PPy hydrogel films

In recent years, the wearable electronic skin (E-skin) has attracted more and more attention due to high sensitivity, good portability and flexibility. In this work, we used the 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-oxidized cellulose nanofibril (TOCN) as the substrate, and used the in-situ polymerization method to introduce polypyrrole (PPy) into the TOCN substrate. Then, the nylon gauze was used as microstructure template to prepare a TOCN/PPy E-skin with a surface microstructure. This E-skin possessed excellent sensing and mechanical properties. In the pressure range of 0–600 Pa, the sensitivity of E-skin was 3.13 kPa⁻¹. In addition, the E-skin exhibited ultrafast response/recovery time (≤10 ms), ultralow detection limit of 0.3 Pa, good stability (>9000 cycles) and mechanical strength of up to 117 MPa. Therefore, the TOCN/PPy E-skin has broad development prospects in the fields of artificial intelligence and health monitoring.     

Embedded silver‐nanowire electrode in an acrylic polymer–silicate nanoparticle composite for highly robust flexible devices

In this study, we explored Ag‐nanowire electrodes embedded on the surface of an elastic acrylic polymer–silicate nanoparticle composite resin (iGloss) for mechanically robust flexible electronic devices. Nanoindentation analysis indicated that the iGloss film was suitable for flexible electronic applications, having modulus and hardness values similar to those of a conventional poly(ethylene terephthalate) (PET) substrate. In situ resistance monitoring for up to 3000 bending cycles revealed that the Ag‐nanowire–iGloss electrode was highly flexible without showing an increase in the resistance. In addition, while a PET substrate carrying Ag nanowires exhibited significantly degraded optical properties with an increase in scratch damage, the Ag‐nanowire–iGloss electrode exhibited superior wear resistance, even when it was subjected to a severe mechanical scratch test. Finally, as a possible application, we demonstrated a flexible, organic, light‐emitting diode with an Ag‐nanowire–iGloss electrode as both the anode and the substrate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45203.