Electrocatalysis in MOF Films for Flexible Electrochemical Sensing: A Comprehensive Review.

Flexible electrochemical sensors can adhere to any bendable surface with conformal contact, enabling continuous data monitoring without compromising the surface's dynamics. Among various materials that have been explored for flexible electronics, metal-organic frameworks (MOFs) exhibit dynamic responses to physical and chemical signals, offering new opportunities for flexible electrochemical sensing technologies. This review aims to explore the role of electrocatalysis in MOF films specifically designed for flexible electrochemical sensing applications, with a focus on their design, fabrication techniques, and applications. We systematically categorize the design and fabrication techniques used in preparing MOF films, including in situ growth, layer-by-layer assembly, and polymer-assisted strategies. The implications of MOF-based flexible electrochemical sensors are examined in the context of wearable devices, environmental monitoring, and healthcare diagnostics. Future research is anticipated to shift from traditional microcrystalline powder synthesis to MOF thin-film deposition, which is expected to not only enhance the performance of MOFs in flexible electronics but also improve sensing efficiency and reliability, paving the way for more robust and versatile sensor technologies.

Wafer-Scale Growth and Transfer of High-Quality MoS2 Array by Interface Design for High-Stability Flexible Photosensitive Device.

Transition metal disulfide compounds (TMDCs) emerges as the promising candidate for new-generation flexible (opto-)electronic device fabrication. However, the harsh growth condition of TMDCs results in the necessity of using hard dielectric substrates, and thus the additional transfer process is essential but still challenging. Here, an efficient strategy for preparation and easy separation-transfer of high-uniform and quality-enhanced MoS2 via the precursor pre-annealing on the designed graphene inserting layer is demonstrated. Based on the novel strategy, it achieves the intact separation and transfer of a 2-inch MoS2 array onto the flexible resin. It reveals that the graphene inserting layer not only enhances MoS2 quality but also decreases interfacial adhesion for easy separation-transfer, which achieves a high yield of ≈99.83%. The theoretical calculations show that the chemical bonding formation at the growth interface has been eliminated by graphene. The separable graphene serves as a photocarrier transportation channel, making a largely enhanced responsivity up to 6.86 mA W-1, and the photodetector array also qualifies for imaging featured with high contrast. The flexible device exhibits high bending stability, which preserves almost 100% of initial performance after 5000 cycles. The proposed novel TMDCs growth and separation-transfer strategy lightens their significance for advances in curved and wearable (opto-)electronic applications.

Centimeter-Scale Tellurium Oxide Films for Artificial Optoelectronic Synapses with Broadband Responsiveness and Mechanical Flexibility.

Prevailing over the bottleneck of von Neumann computing has been significant attention due to the inevitableness of proceeding through enormous data volumes in current digital technologies. Inspired by the human brain's operational principle, the artificial synapse of neuromorphic computing has been explored as an emerging solution. Especially, the optoelectronic synapse is of growing interest as vision is an essential source of information in which dealing with optical stimuli is vital. Herein, flexible optoelectronic synaptic devices composed of centimeter-scale tellurium dioxide (TeO2) films detecting and exhibiting synaptic characteristics to broadband wavelengths are presented. The TeO2-based flexible devices demonstrate a comprehensive set of emulating basic optoelectronic synaptic characteristics; i.e., excitatory postsynaptic current (EPSC), paired-pulse facilitation (PPF), conversion of short-term to long-term memory, and learning/forgetting. Furthermore, they feature linear and symmetric conductance synaptic weight updates at various wavelengths, which are applicable to broadband neuromorphic computations. Based on this large set of synaptic attributes, a variety of applications such as logistic functions or deep learning and image recognition as well as learning simulations are demonstrated. This work proposes a significant milestone of wafer-scale metal oxide semiconductor-based artificial synapses solely utilizing their optoelectronic features and mechanical flexibility, which is attractive toward scaled-up neuromorphic architectures.

Analysis of a Flexible Photoconductor, Manufactured with Organic Semiconductor Films.

This work presents the evaluation of the electrical behavior of a flexible photoconductor with a planar heterojunction architecture made up of organic semiconductor films deposited by high vacuum evaporation. The heterojunction was characterized in its morphology and mechanical properties by scanning electron microscopy and atomic force microscopy. The electrical characterization was carried out through the approximations of ohmic and SCLC (Space-Charge Limited Current) behaviors using experimental J-V (current density-voltage) curves at different voltages and under different light conditions. The optimization of the photoconductor was carried out through annealing and accelerated lighting processes. With these treatments, the Knoop Hardness of the flexible photoconductor has reached a value of 8 with a tensile strength of 5.7 MPa. The ohmic and SCLC approximations demonstrate that the unannealed device has an ohmic behavior, whereas the annealed device has an SCLC behavior, and after the optimization process, an ohmic behavior and a maximum current density of 0.34 mA/mm2 were obtained under blue light. The approximations of the device's electron mobility (µn) and free carrier density (n0) were performed under different light conditions, and the electrical activation energy and electrical gap were obtained for the flexible organic device, resulting in appropriate properties for these applications.

Flexible multifunctional titania nanotube array platform for biological interfacing.

Abstract: The current work presents a novel flexible multifunctional platform for biological interface applications. The use of titania nanotube arrays (TNAs) as a multifunctional material is explored for soft-tissue interface applications. In vitro biocompatibility of TNAs to brain-derived cells was first examined by culturing microglia cells-the resident immune cells of the central nervous system on the surface of TNAs. The release profile of an anti-inflammatory drug, dexamethasone from TNAs-on-polyimide substrates, was then evaluated under different bending modes. Flexible TNAs-on-polyimide sustained a linear release of anti-inflammatory dexamethasone up to ~11 days under different bending conditions. Finally, microfabrication processes for patterning and transferring TNA microsegments were developed to facilitate structural stability during device flexing and to expand the set of compatible polymer substrates. The techniques developed in this study can be applied to integrate TNAs or other similar nanoporous inorganic films onto various polymer substrates. Impact statement: Titania nanotube arrays (TNAs) are highly tunable and biocompatible structures that lend themselves to multifunctional implementation in implanted devices. A particularly important aspect of titania nanotubes is their ability to serve as nano-reservoirs for drugs or other therapeutic agents that slowly release after implantation. To date, TNAs have been used to promote integration with rigid, dense tissues for dental and orthopedic applications. This work aims to expand the implant applications that can benefit from TNAs by integrating them onto soft polymer substrates, thereby promoting compatibility with soft tissues. The successful direct growth and integration of TNAs on polymer substrates mark a critical step toward developing mechanically compliant implantable systems with drug delivery from nanostructured inorganic functional materials. Diffusion-driven release kinetics and the high drug-loading efficiency of TNAs offer tremendous potential for sustained drug delivery for scientific investigations, to treat injury and disease, and to promote device integration with biological tissues. This work opens new opportunities for developing novel and more effective implanted devices that can significantly improve patient outcomes and quality of life. Supplementary information: The online version contains supplementary material available at 10.1557/s43577-023-00628-y.

A 2.5 V In-Plane Flexi-Pseudocapacitor with Unprecedented Energy and Cycling Efficiency for All-Weather Applications.

As electronic devices for aviation, space, and satellite applications become more sophisticated, built-in energy storage devices also require a wider temperature spectrum. Herein, an all-climate operational, energy and power-dense, flexible, in-plane symmetric pseudocapacitor is demonstrated with utmost operational safety and long cycle life. The device is constructed with interdigital-patterned laser-scribed carbon-supported electrodeposited V5O12·6H2O as a binder-free electrode and a novel high-voltage anti-freezing water-in-salt-hybrid electrolyte. The anti-freezing electrolyte can operate over a wide temperature range of -40-60 °C while offering a stable potential window of ≈2.5 V. The device undergoes rigorous testing under diverse environmental conditions, including rapid and regular temperature and mechanical transition over multiple cycles. Additionally, detailed theoretical simulation studies are performed to understand the interfacial interactions with the active material as well as the local behavior of the anti-freeze electrolyte at different temperatures. As a result, the all-weather pseudocapacitor at 1 A g-1 shows a high areal capacitance of 234.7 mF cm-2 at room temperature and maintains a high capacitance of 129.8 mF cm-2 even at -40 °C. Besides, the cell operates very reliably for over 80 950 cycles with a capacitance of 25.7 mF cm-2 at 10 A g-1 and exhibits excellent flexibility and bendability under different stress conditions.

Adaptive Gap-Tunable Surface-Enhanced Raman Spectroscopy.

Gap plasmon (GP) resonance in static surface-enhanced Raman spectroscopy (SERS) structures is generally too narrow and not tunable. Here, we present an adaptive gap-tunable SERS device to selectively enhance and modulate different vibrational modes via active flexible Au nanogaps, with adaptive optical control. The tunability of GP resonance is up to ∼1200 cm-1 by engineering gap width, facilitated by mechanical bending of a polyethylene terephthalate substrate. We confirm that the tuned GP resonance selectively enhances different Raman spectral regions of the molecules. Additionally, we dynamically control the SERS intensity through the wavefront shaping of excitation beams. Furthermore, we demonstrate simulation results, exhibiting the mechanical and optical properties of a one-dimensional flexible nanogap and their advantage in high-speed biomedical sensing. Our work provides a unique approach for observing and controlling the enhanced chemical responses with dynamic tunability.

Covalently-Bonded Laminar Assembly of Van der Waals Semiconductors with Polymers: Toward High-Performance Flexible Devices.

Van der Waals semiconductors (vdWS) offer superior mechanical and electrical properties and are promising for flexible microelectronics when combined with polymer substrates. However, the self-passivated vdWS surfaces and their weak adhesion to polymers tend to cause interfacial sliding and wrinkling, and thus, are still challenging the reliability of vdWS-based flexible devices. Here, an effective covalent vdWS-polymer lamination method with high stretch tolerance and excellent electronic performance is reported. Using molybdenum disulfide (MoS2 )and polydimethylsiloxane (PDMS) as a case study, gold-chalcogen bonding and mercapto silane bridges are leveraged. The resulting composite structures exhibit more uniform and stronger interfacial adhesion. This enhanced coupling also enables the observation of a theoretically predicted tension-induced band structure transition in MoS2 . Moreover, no obvious degradation in the devices' structural and electrical properties is identified after numerous mechanical cycle tests. This high-quality lamination enhances the reliability of vdWS-based flexible microelectronics, accelerating their practical applications in biomedical research and consumer electronics.

Gallium-Based Liquid Metals in Rechargeable Batteries: From Properties to Applications.

Gallium-based (Ga-based) liquid metals have attracted considerable interest due to their low melting points, enabling them to feature both liquid properties and metallic properties at room temperature. In light of this, Ga-based liquid metals also possess excellent deformability, high electrical and thermal conductivity, superior metal affinity, and unique self-limited surface oxide, making them popular functional materials in energy storage. This provides a possibility to construct high-performance rechargeable batteries that are deformable, free of dendrite growth, and so on. This review primarily starts with the property of Ga-based liquid metal, and then focuses on the potential applications in rechargeable batteries by exploiting these advantages, aiming to construct the correlation between properties and structures. The glorious applications contain interface protection, self-healing electrode construction, thermal management, and flexible batteries. Finally, the opportunities and obstacles for the applications of liquid metal in batteries are presented.

Defect Synergistic Regulations of Li&Na Co-Doped Flexible Cu2 ZnSn(S,Se)4 Solar Cells Achieving over 10% Certified Efficiency.

Ion doping is an effective strategy for achieving high-performance flexible Cu2 ZnSn(S,Se)4 (CZTSSe) solar cells by defect regulations. Here, a Li&Na co-doped strategy is applied to synergistically regulate defects in CZTSSe bulks. The quality absorbers with the uniformly distributed Li and Na elements are obtained using the solution method, where the acetates (LiAc and NaAc) are as additives. The concentration of the harmful CuZn anti-site defects is decreased by 8.13% after Li incorporation, and that of the benign NaZn defects is increased by 36.91% after Na incorporation. Synergistic Li&Na co-doping enhances the carrier concentration and reduces the interfacial defects concentration by one order of magnitude. As a result, the flexible CZTSSe solar cell achieves a power conversion efficiency (PCE) of 10.53% with certified 10.12%. Because of the high PCE and the homogeneous property, the Li&Na co-doped device is fabricated to a large area (2.38 cm2 ) and obtains 9.41% PCE. The co-doping investigation to synergistically regulate defects provides a new perspective for efficient flexible CZTSSe solar cells.

Single-crystalline GaN microdisk arrays grown on graphene for flexible micro-LED application.

We report the growth of single-crystalline GaN microdisk arrays on graphene and their application in flexible light-emitting diodes (LEDs). Graphene layers were directly grown onc-sapphire substrates using chemical vapor deposition and employed as substrates for GaN growth. Position-controlled GaN microdisks were laterally overgrown on the graphene layers with a micro-patterned SiO2mask using metal-organic vapor-phase epitaxy. The as-grown GaN microdisks exhibited excellent single crystallinity with a uniform in-plane orientation. Furthermore, we fabricated flexible micro-LEDs by achieving heteroepitaxial growth ofn-GaN, InxGa1-xN/GaN multiple quantum wells, andp-GaN layers on graphene-coated sapphire substrates. The GaN micro-LED arrays were successfully transferred onto bendable substrates and displayed strong blue light emission under room illumination, demonstrating their potential for integration into flexible optoelectronic devices.

A BTO/PVDF/PDMS Piezoelectric Tangential and Normal Force Sensor Inspired by a Wind Chime.

There is a growing demand for flexible pressure sensors in environmental monitoring and human-robot interaction robotics. A flexible and susceptible sensor can discriminate multidirectional pressure, thus effectively detecting signals of small environmental changes and providing solutions for personalized medicine. This paper proposes a multidimensional force detection sensor inspired by a wind chime structure with a three-dimensional force structure to detect and analyze normal and shear forces in real time. The force-sensing structure of the sensor consists of an upper and lower membrane on a polydimethylsiloxane substrate and four surrounding cylinders. A piezoelectric hemisphere is made of BTO/PVDF/PDMS composite material. The sensor columns in the wind chime structure surround the piezoelectric layer in the middle. When pressure is applied externally, the sensor columns are connected to the piezoelectric layer with a light touch. The piezoelectric hemisphere generates a voltage signal. Due to the particular structure of the sensor, it can accurately capture multidimensional forces and identify the direction of the external force by analyzing the position of the sensor and the output voltage amplitude. The development of such sensors shows excellent potential for self-powered wearable sensors, human-computer interaction, electronic skin, and soft robotics applications.

Fabrication of Flexible PDMS Films with Micro-Convex Structure for Light Extraction from Organic Light-Emitting Diodes.

In this study, we demonstrated organic light-emitting diodes (OLEDs) outcoupling with a flexible polydimethylsiloxane (PDMS) film with a micro-convex structure using the breath figure (BF) method. We can easily control the micro-convex pattern by adjusting the concentration of polystyrene and the humidity during the BF process. As process conditions to fabricate the micro-convex structure, polymer concentrations of 10, 20, 40, and 80 mg/mL and 60, 70, and 80% relative humidity were used. To evaluate the optical properties, we analyzed the transmission, diffusion, and electroluminescence with or without the micro-convex structure on the OLEDs. The shape and density of the micro-convex structure are related to its optical properties and outcoupling and we have experimentally demonstrated this. By applying a micro-convex structure, it achieved up to a 42% improvement in the external quantum efficiency compared to bare OLEDs (without any light extraction film). We expect the fabricated flexible light extraction film to be effective for outcoupling and applicable to flexible devices.

Direct Current Treatment Tuning Crystallinity Leading to High-Performance p-Type Sb2Te3 Flexible Thin Films.

With the development of wearable electronics, inorganic flexible thin films (f-TFs) with high thermoelectric performance have attracted increasing research interest. To further enhance the thermoelectric performance of p-type inorganic Sb2Te3-based f-TFs, we employed direct current treatment to tune the crystallinity by rationally tuning the direct current treatment time. Correspondingly, a high electrical conductivity of >845 S cm-1 and a moderate Seebeck coefficient of >110 µV K-1 within the entire measurement temperature range have been simultaneously achieved. Consequently, a high power factor of 12.84 µW cm-1 K-2 at 423 K has been realized in the as-prepared p-type Sb2Te3 f-TF treated by a direct current of 5 A for 4 min. A flexible thermoelectric device has been further assembled to demonstrate the power-generating capacity. This study indicates that the direct current treatment is an effective method to improve the thermoelectric performance of Sb2Te3 f-TFs.

Nanoengineering Approach toward High Power Factor Ag2Se/Se Composite Films for Flexible Thermoelectric Generators.

Herein, a flexible Ag2Se/Se composite film with a high power factor has been fabricated on a nylon membrane. The film has a high density and contains well-crystallized Ag2Se grains and embedded Se nanoinclusions, which exhibits not only excellent flexibility but also a comparably large room-temperature power factor and Seebeck coefficient of up to 2023 µW m-1 K-2 and -155 µV K-1, respectively. The high Seebeck coefficient is ascribed to the energy-filtering effect as caused by the Se/Ag2Se heterointerface. The assembled flexible thermoelectric generator (4-leg) exhibits a maximum output power of 1135 nW and a power density of up to 16.4 W m-2 when the applied temperature difference is 30 K. This work offers a feasible method to design high-performance and low-cost flexible thermoelectric generators used for wearable electronics.

Centimeter-Transferable III-Nitride Membrane Enabled by Interfacial Adhesion Control for a Flexible Photosensitive Device.

Flexible III-nitride-based optoelectronic devices are crucial for the next-generation foldable/wearable lighting sterilization and sensor working in the ultraviolet (UV) region. However, the strong bonding effect at the epitaxial interface of III-nitride and bare sapphire substrate makes it difficult for epilayer separation and flexible applications. Although the emerging van der Waals epitaxy (vdWE) with graphene insertion layer offers a feasible route for weakening the interfacial adhesion, the intact centimeter-transferable III-nitride membrane still remains challenging. The spontaneous delamination occurs due to the too weak interfacial adhesion of pure vdW force, and on the contrary, the structural damage of graphene by high-temperature hydrogen etching during the III-nitride growth might also cause separation failure. Up to now, the efficient control of vdWE interfacial adhesion is still an on-going research hotspot. Herein, we demonstrate the interfacial adhesion control of III-nitride vdWE by utilizing graded high-temperature nitridation treatment of the graphene insertion layer, which generates defects and N doping in different levels. The corresponding epitaxial modes of pure-vdWE, quasi-vdWE, and mixed epitaxy are achieved according to the interfacial adhesion difference. It reveals that the quasi-vdWE enabled by small graphene defects and proper N doping triggers the low formation energy for AlN nucleation; meanwhile, the proper interfacial adhesion ensures the growth integrality and intact separation of III-nitride membrane in the centimeter scale. The UV resin-assisted bonding technique is proposed for the successful transfer of III-nitride onto a flexible substrate. The flexible photodetector is fabricated by using a graphene monolayer as the photocarrier transport channel, and it achieves a high device yield of 90%, retaining ∼60% of its initial performance after 250 bending cycles. This work offers the promising strategy for controlling vdWE interfacial adhesion, and the separable and transferable III-nitride membrane lays the foundation for advances of future UV foldable and wearable devices.

An Ultrathin Flexible Programmable Spin Logic Device Based on Spin-Orbit Torque.

Flexible electronic devices have shown increasingly promising value facilitating our daily lives. However, flexible spintronic devices remain in their infancy. Here, this research demonstrates a type of nonvolatile, low power dissipation, and programmable flexible spin logic device, which is based on the spin-orbit torque in polyimide (PI)/Ta/Pt/Co/Pt heterostructures fabricated via capillary-assisted electrochemical delamination. The magnetization switching ratio is shown to be about 50% for the flexible device and does not change after 100 cycles of bending, indicating the device has stable performance. By designing the path of pulse current, five Boolean logic gates AND, NAND, NOT, NOR, and OR can be realized in an integrated two-element device. Moreover, such peeling-off devices can be successfully transferred to almost any substrate, such as paper and human skin, and maintain high performance. The flexible PI/Ta/Pt/Co/Pt spin logic device serves as logic-in-memory architecture and can be used in wearable electronics.

Highly Flexible Triboelectric Nanogenerator Using Porous Carbon Nanotube Composites.

The rapid development of portable and wearable electronic devices has led researchers to actively study triboelectric nanogenerators (TENGs) that can provide self-powering capabilities. In this study, we propose a highly flexible and stretchable sponge-type TENG, named flexible conductive sponge triboelectric nanogenerator (FCS-TENG), which consists of a porous structure manufactured by inserting carbon nanotubes (CNTs) into silicon rubber using sugar particles. Nanocomposite fabrication processes, such as template-directed CVD and ice freeze casting methods for fabricating porous structures, are very complex and costly. However, the nanocomposite manufacturing process of flexible conductive sponge triboelectric nanogenerators is simple and inexpensive. In the tribo-negative CNT/silicone rubber nanocomposite, the CNTs act as electrodes, increasing the contact area between the two triboelectric materials, increasing the charge density, and improving charge transfer between the two phases. Measurements of the performance of flexible conductive sponge triboelectric nanogenerators using an oscilloscope and a linear motor, under a driving force of 2-7 N, show that it generates an output voltage of up to 1120 V and a current of 25.6 µA. In addition, by using different weight percentages of carbon nanotubes (CNTs), it is shown that the output power increases with the weight percentage of carbon nanotubes (CNTs). The flexible conductive sponge triboelectric nanogenerator not only exhibits good performance and mechanical robustness but can also be directly used in light-emitting diodes connected in series. Furthermore, its output remains extremely stable even after 1000 bending cycles in an ambient environment. In sum, the results demonstrate that flexible conductive sponge triboelectric nanogenerators can effectively power small electronics and contribute to large-scale energy harvesting.

Stretchable and Skin-Mountable Temperature Sensor Array Using Reduction-Controlled Graphene Oxide for Dermatological Thermography.

Since thermometry of human skin is critical information that provides important aspects of human health and physiology, accurate and continuous temperature measurement is required for the observation of physical abnormalities. However, conventional thermometers are uncomfortable because of their bulky and heavy features. In this work, we fabricated a thin, stretchable array-type temperature sensor using graphene-based materials. Furthermore, we controlled the degree of graphene oxide reduction and enhanced the temperature sensitivity. The sensor exhibited an excellent sensitivity of 2.085% °C-1. The overall device was designed in a wavy meander shape to provide stretchability for the device so that precise detection of skin temperature could be performed. Furthermore, polyimide film was coated to secure the chemical and mechanical stabilities of the device. The array-type sensor enabled spatial heat mapping with high resolution. Finally, we introduced some practical applications of skin temperature sensing, suggesting the possibility of skin thermography and healthcare monitoring.