Rapid Prototyping for Soft‐Matter Electronics

A series of rapid and inexpensive methods to produce elastically soft sensors and circuits in minutes using a CO₂ laser (10.6 μm wavelength) are introduced. These soft‐matter electronics are composed of laser‐patterned films of conductive poly(dimethylsiloxane) (cPDMS) and liquid‐phase gallium–indium (GaIn) alloy embedded in a thin sheet of soft silicone elastomer. Direct laser patterning eliminates the need for photolithography, replica molding, and customized inkjet or microcontact (μCP) printing, and allows conductive traces of cPDMS and liquid GaIn to be rapidly integrated into a single soft‐matter circuit. The versatility of this fabrication method is demonstrated by the production of a variety of electrically functional soft‐matter sensors and circuit elements that contain features with >150 μm planar dimensions. It is postulate that in the case of GaIn alloy patterning occurs when the recoil force of the escaping vapor exceeds the liquid's surface tension. This mechanism exploits the unique “moldability” of liquid GaIn alloy, which forms a surface oxide of Ga₂O₃ that allows the patterned film to maintain its shape.     

Room‐Temperature Printing of Organic Thin‐Film Transistors with π‐Junction Gold Nanoparticles

Printing semiconductor devices under ambient atmospheric conditions is a promising method for the large‐area, low‐cost fabrication of flexible electronic products. However, processes conducted at temperatures greater than 150 °C are typically used for printed electronics, which prevents the use of common flexible substrates because of the distortion caused by heat. The present report describes a method for the room‐temperature printing of electronics, which allows thin‐film electronic devices to be printed at room temperature without the application of heat. The development of π‐junction gold nanoparticles as the electrode material permits the room‐temperature deposition of a conductive metal layer. Room‐temperature patterning methods are also developed for the Au ink electrodes and an active organic semiconductor layer, which enables the fabrication of organic thin‐film transistors through room‐temperature printing. The transistor devices printed at room temperature exhibit average field‐effect mobilities of 7.9 and 2.5 cm² V^?1 s^?1 on plastic and paper substrates, respectively. These results suggest that this fabrication method is very promising as a core technology for low‐cost and high‐performance printed electronics.     

A Novel Conductive Core–Shell Particle Based on Liquid Metal for Fabricating Real‐Time Self‐Repairing Flexible Circuits

As a critical part of flexible electronics, flexible circuits inevitably work in a dynamic state, which causes electrical deterioration of brittle conductive materials (i.e., Cu, Ag, ITO). Recently, gallium‐based liquid metal particles (LMPs) with electrical stability and self‐repairing have been studied to replace brittle materials owing to their low modulus and excellent conductivity. However, LMP‐coated Ga₂O₃ needs to activate by external sintering, which makes it more complicated to fabricate and gives it a larger short‐circuit risk. Core–shell structural particles (Ag@LMPs) that exhibit excellent initial conductivity(8.0 Ω sq^?1) without extra sintering are successfully prepared by coating nanosilver on the surface of LMPs through in situ chemical reduction. The critical stress at which rigid Ag shells rupture can be controlled by adjusting the Ag shell thickness so that LM cores with low moduli can release, achieving real‐time self‐repairing (within 200 ms) under external destruction. Furthermore, a flexible circuit utilizing Ag@LMPs is fabricated by screen printing, and exhibits outstanding stability and durability (R/R₀ < 1.65 after 10 000 bending cycles in a radius of 0.5 mm) because of the functional core–shell structure. The self‐repairable Ag@LMPs prepared in this study are a candidate filler for flexible circuit design through multiple processing methods.     

Facile and Rapid Method for Fabricating Liquid Metal Electrodes with Highly Precise Patterns via One‐Step Coating

Gallium‐based alloys, which are virtually non‐toxic liquid metals at room temperature, are considered highly promising electrode materials for state‐of‐the‐art electronics with new form factors. Herein, a facile and rapid method to fabricate liquid metal electrodes with highly precise patterns via a one‐step coating is presented. For this work, polymeric stencil masks with dual structures, comprising upper and lower structures for injecting and molding the liquid metal, respectively, are used for direct patterning of the liquid metal via spray deposition for few seconds, enabling the formation of complex and minute patterns including long thin lines and hollow forms. This method can be adapted to 3D substrates of various materials without any surface treatment, owing to the intrinsic adhesive and flexible properties of the polymeric masks ensuring conformal contact with non‐flat surfaces, and is also expected to be applicable to sub‐micron patterns. In addition, a number of highly flexible/stretchable electronic applications, exhibiting no change in electrical conductivity upon consecutive structural deformations, are demonstrated on various substrates including human skin. It is anticipated that these results will not only spur the further development of flexible/stretchable electronics, but also significantly contribute to the innovative on‐site fabrication of wearable electronics with high durability.     

Constructing Conductive Interfaces between Nickel Oxide Nanocrystals and Polymer Carbon Nitride for Efficient Electrocatalytic Oxygen Evolution Reaction

Combining transition metal oxide catalysts with conductive carbonaceous material is a feasible way to improve the conductivity. However, the electrocatalytic performance is usually not distinctly improved because the interfacial resistance between metal oxides and carbon is still large and thereby hinders the charge transport in catalysis. Herein, the conductive interface between poorly conductive NiO nanoparticles and semi‐conductive carbon nitride (CN) is constructed. The NiO/CN exhibits much‐enhanced oxygen evolution reaction (OER) performance than corresponding NiO and CN in electrolytes of KOH solution and phosphate buffer saline, which is also remarkably superior over NiO/C, commercial RuO₂, and mostly reported NiO‐based catalysts. X‐ray photoelectron spectroscopy and extended X‐ray absorption fine structure spectrum reveal that a metallic Ni–N bond is formed between NiO and CN. Density functional theory calculations suggest that NiO and CN linked by a Ni–N bond possess a low Gibbs energy for OER intermediate adsorptions, which not only improves the transfer of charge but also promotes the transmission of mass in OER. The metal–nitrogen bonded conductive and highly active interface pervasively exists between CN and other transition metal oxides including Co₃O₄, CuO, and Fe₂O₃, making it promising as an inexpensive catalyst for efficient water splitting.     

Metal‐Organic Framework Nanofilm for Mechanically Flexible Information Storage Applications

Metal‐organic frameworks (MOFs), which are formed by association of metal cations or clusters of cations (“nodes”) with soft organic bridging ligands (“linkers”), are a fascinating class of flexible crystalline hybrid materials offering potential strategy for the construction of flexible electronics. In this study, a high‐quality MOF nanofilm, HKUST‐1, on flexible gold‐coated polyethylene terephthalate substrates is fabricated using liquid phase epitaxy approach. Uniform and reproducible resistive switching effect, which can be sustained under the strain of as high as 2.8%, and over the wide temperature range of –70 to +70 °C, is observed for the first time in the all solid‐state Au/HKUST‐1/Au/thin film structures. Through conductive atomic force microscopic and depth‐profiling X‐ray photoelectron spectroscopicanalysis, it is proposed that the electric field‐induced migration of the Cu_­²⁺ ions, which may lead to subsequent pyrolysis of the trimesic acid linkers and thus the formation of highly conducting filaments, could be the possible origin for the observed uniform resistance switching in HKUST‐1 nanofilms.     

Stretchable‐Fiber‐Confined Wetting Conductive Liquids as Wearable Human Health Monitors

Wetting behaviors on stretchable supports are very common in our daily lives, however, received limited attention even they show promising potentials in flexible electronics and other fields. In this study, stretchable wetting behaviors of conductive liquids deposited onto two horizontal rubber fibers are investigated. A firm liquid/solid interaction during the stretching process can contribute to a stable liquid bridge between the fibers even under extremely stretching, showing their proof‐to‐principle ability to monitor human movement toward early diagnosis of Parkinson's disease or sports injury prevention.     

Liquid‐Metal Electrode for High‐Performance Triboelectric Nanogenerator at an Instantaneous Energy Conversion Efficiency of 70.6%

Harvesting ambient mechanical energy is a key technology for realizing self‐powered electronics, which has tremendous applications in wireless sensing networks, implantable devices, portable electronics, etc. The currently reported triboelectric nanogenerator (TENG) mainly uses solid materials, so that the contact between the two layers cannot be 100% with considering the roughness of the surfaces, which greatly reduces the total charge density that can be transferred and thus the total energy conversion efficiency. In this work, a liquid‐metal‐based triboelectric nanogenerator (LM‐TENG) is developed for high power generation through conversion of mechanical energy, which allows a total contact between the metal and the dielectric. Due to that the liquid–solid contact induces large contacting surface and its shape adaptive with the polymer thin films, the LM‐TENG exhibits a high output charge density of 430 μC m^?2, which is four to five times of that using a solid thin film electrode. And its power density reaches 6.7 W m^?2 and 133 kW m^?3. More importantly, the instantaneous energy conversion efficiency is demonstrated to be as high as 70.6%. This provides a new approach for improving the performance of the TENG for special applications. Furthermore, the liquid easily fluctuates, which makes the LM‐TENG inherently suitable for vibration energy harvesting.     

Catalytic Metal Foam by Chemical Melting and Sintering of Liquid Metal Nanoparticles

Metal foams are highly sought‐after porous structures for heterogeneous catalysis, which are fabricated by templating, injecting gas, or admixing blowing agents into a metallic melt at high temperatures. They also require additional catalytic material coating. Here, a low‐melting‐point liquid metal is devised for the single‐step formation of catalytic foams in mild aqueous environments. A hybrid catalytic foam fabrication process is presented via simultaneous chemical foaming, melting, and sintering reaction of liquid metal nanoparticles. As a model, nanoparticles of tertiary low‐melting‐point eutectic alloy of indium, bismuth, and tin (Field's metal) are processed with sodium hydrogen carbonate, an environmentally benign blowing agent. The competing endothermic foaming and exothermic sintering reactions are triggered by an aqueous acidic bath. The overall foaming process occurs at a localized temperature above 200 °C, producing submicron‐ to micron‐sized open‐cell pore foams with conductive cores and semiconducting surface decorations. The catalytic properties of the metal foams are explored for a range of applications including photo‐electrocatalysis, bacteria electrofiltration, and CO₂ electroconversion. In particular, the Field's metal‐based foams show exceptional CO₂ electrochemical conversion performance at low applied voltages. The facile process presented here can be extended to other low‐temperature post transition and transition metal alloys.     

Flexible and Multifunctional Silk Textiles with Biomimetic Leaf‐Like MXene/Silver Nanowire Nanostructures for Electromagnetic Interference Shielding,Humidity Monitoring,and Self‐Derived Hydrophobicity

Although flexible and multifunctional textiles are promising for wearable electronics and portable device applications, the main issue is to endow textiles with multifunctionalities while maintaining their innate flexible and porous features. Herein, a vacuum‐assisted layer‐by‐layer assembly technique is demonstrated to conformally deposit electrically conductive substances on textiles for developing multifunctional and flexible textiles with superb electromagnetic interference (EMI) shielding performances, superhydrophobicity, and highly sensitive humidity response. The formed leaf‐like nanostructure is composed of silver nanowires (AgNWs) as the highly conductive skeleton (vein) and transition metal carbide/carbonitride (MXene) nanosheets as the lamina. The presence of MXene protects AgNWs from oxidation and enhances the combination of AgNWs with the fabric substrate, and the transformation of its functional groups leads to self‐derived hydrophobicity. The flexible and multifunctional textile exhibits a low sheet resistance of 0.8 Ω sq^?1, outstanding EMI shielding efficiency of 54 dB in the X‐band at a small thickness of 120 µm, and highly sensitive humidity responses, while retaining its satisfactory porosity and permeability. The self‐derived hydrophobicity with a large contact angle of >140° is achieved by aging the hydrophilic MXene coated silk. The wearable multifunctional textiles are highly promising for applications in intelligent garments, humidity sensors, actuators, and EMI shielding.     

Rational Design of a Printable,Highly Conductive Silicone‐based Electrically Conductive Adhesive for Stretchable Radio‐Frequency Antennas

Stretchable radio‐frequency electronics are gaining popularity as a result of the increased functionality they gain through their flexible nature, impossible within the confines of rigid and planar substrates. One approach to fabricating stretchable antennas is to embed stretchable or flowable conductive materials, such as conductive polymers, conductive polymer composites, and liquid metal alloys as stretchable conduction lines. However, these conductive materials face many challenges, such as low electrical conductivity under mechanical deformation and delamination from substrates. In the present study, a silicone‐based electrically conductive adhesive (silo‐ECA) is developed that have a conductivity of 1.51 × 10⁴ S cm^?1 and can maintain conductivity above 1.11 × 10³ S cm^?1, even at a large stain of 240%. By using the stretchable silo‐ECAs as a conductor pattern and pure silicone elastomers as a base substrate, stretchable antennas can be fabricated by stencil printing or soft‐lithography. The resulting antenna's resonant frequency is tunable over a wide range by mechanical modulation. This fabrication method is low‐cost, can support large‐scale production, has high reliability over a wide temperature range, and eliminates the concerns of leaking or delamination between conductor and substrate experienced in previously reported micro‐fluidic antennas.     

Iron Fluoride–Carbon Nanocomposite Nanofibers as Free‐Standing Cathodes for High‐Energy Lithium Batteries

The development of low‐cost, high‐energy cathodes from nontoxic, broadly available resources is a big challenge for the next‐generation rechargeable lithium or lithium‐ion batteries. As a promising alternative to traditional intercalation‐type chemistries, conversion‐type metal fluorides offer much higher theoretical capacity and energy density than conventional cathodes. Unfortunately, these still suffer from irreversible structural degradation and rapid capacity fading upon cycling. To address these challenges, here a versatile and effective strategy is harnessed for the development of metal fluoride–carbon (C) nanocomposite nanofibers as flexible, free‐standing cathodes. By taking iron trifluoride (FeF₃) as a successful example, assembled FeF₃–C/Li cells with a high reversible FeF₃ capacity of 550 mAh g^?1 at 100 mA g^?1 (three times that of traditional cathodes, such as lithium cobalt oxide, lithium nickel cobalt aluminum oxide, and lithium nickel cobalt manganese oxide) and excellent stability (400+ cycles with little‐to‐no degradation) are demonstrated. The promising characteristics can be attributed to the nanoconfinement of FeF₃ nanoparticles, which minimizes the segregation of Fe and LiF upon cycling, the robustness of the electrically conductive C network and the prevention of undesirable reactions between the active material and the liquid electrolyte using the composite design and electrolyte selection.     

Nonprecious Intermetallic Al7Cu4Ni Nanocrystals Seamlessly Integrated in Freestanding Bimodal Nanoporous Copper for Efficient Hydrogen Evolution Catalysis

Tremendous demands for renewable hydrogen generated from water splitting have stimulated intensive research on developing earth‐abundant, non‐noble, and versatile metal catalysts toward the hydrogen evolution reactions (HER). Here, self‐supported Cu‐Ni‐Al hybrid electrodes that are composed of electroactive Al₇Cu₄Ni@Cu₄Ni core/shell nanocrystals seamlessly integrated in self‐supported 3D bimodal nanoporous Cu skeleton (Bi‐NP Cu/Al₇Cu₄Ni@Cu₄Ni) as robust HER electrocatalysts in alkaline electrolyte are reported. As a result of the proper architecture, in which the Bi‐NP Cu skeleton not only facilitates both electron and electrolyte transports but also provides high specific surface areas to fully use high electrocatalytic activity of Al₇Cu₄Ni@Cu₄Ni core/shell nanocrystals, the Bi‐NP Cu/Al₇Cu₄Ni@Cu₄Ni hybrid catalysts exhibit a low onset overpotential of 60 mV and a small Tafel slope of 110 mV dec^?1, enabling the catalytic current density of 10 mA cm^?2 at a low overpotential of 139 mV. The highly stable electrochemical performance makes them promising candidates as cathode catalysts in alkaline‐based devices.     

Heat‐Free Fabrication of Metallic Interconnects for Flexible/Wearable Devices

Exploiting interfacial excess (Γ), Laplace pressure jump (ΔP), surface work, and coupling them to surface reactivity have led to the synthesis of undercooled metal particles. Metastability is maintained by a core–shell particle architecture. Fracture of the thin shell leads to solidification with concomitant sintering. Applying Scherer's constitutive model for load‐driven viscous sintering on the undercooled particles implies that they can form conductive traces. Combining metastability to eliminate heat and robustness of viscous sintering, an array of conductive metallic traces can be prepared, leading to plethora of devices on various flexible and/or heat sensitive substrates. Besides mechanical sintering, chemical sintering can be performed, which negates the need of either heat or load. In the latter, connectivity is hypothesized to occur via a Frenkel's theory of sintering type mechanism. This work reports heat‐free, ambient fabrication of metallic conductive interconnects and traces on all types of substrates.     

Microstructure and Electrical Properties of Low Temperature Processed Ohmic Contacts to p‐Type GaN

With Ni/Au and Pd/Au metal schemes and low temperature processing, we formed low resistance stable Ohmic contacts to p‐type GaN. Our investigation was preceded by conventional cleaning, followed by treatment in boiling HNO₃:HCl (1:3). Metallization was by thermally evaporating 30 nm Ni/15 nm Au or 25 nm Pd/15 nm Au. After heat treatment in O₂ + N₂ at various temperatures, the contacts were subsequently cooled in liquid nitrogen. Cryogenic cooling following heat treatment at 600 ·C decreased the specific contact resistance from 9.84·10^?4 Ωcm² to 2.65·10^?4 Ωcm² for the Ni/Au contacts, while this increased it from 1.80·10^?4 Ωcm² to 3.34·10^?4 Ωcm² for the Pd/Au contacts. The Ni/Au contacts showed slightly higher specific contact resistance than the Pd/Au contacts, although they were more stable than the Pd contacts. X‐ray photoelectron spectroscopy depth profiling showed the Ni contacts to be NiO followed by Au at the interface for the Ni/Au contacts, whereas the Pd/Au contacts exhibited a Pd:Au solid solution. The contacts quenched in liquid nitrogen following sintering were much more uniform under atomic force microscopy examination and gave a 3 times lower contact resistance with the Ni/Au design. Current‐voltage‐temperature analysis revealed that conduction was predominantly by thermionic field emission.     

Conductive adhesive with transient liquid‐phase sintering technology for high‐power device applications

A highly reliable conductive adhesive obtained by transient liquid‐phase sintering (TLPS) technologies is studied for use in high‐power device packaging. TLPS involves the low‐temperature reaction of a low‐melting metal or alloy with a high‐melting metal or alloy to form a reacted metal matrix. For a TLPS material (consisting of Ag‐coated Cu, a Sn96.5‐Ag3.0‐Cu0.5 solder, and a volatile fluxing resin) used herein, the melting temperature of the metal matrix exceeds the bonding temperature. After bonding of the TLPS material, a unique melting peak of TLPS is observed at 356 °C, consistent with the transient behavior of Ag₃Sn + Cu₆Sn₅ → liquid + Cu₃Sn reported by the National Institute of Standards and Technology. The TLPS material shows superior thermal conductivity as compared with other commercially available Ag pastes under the same specimen preparation conditions. In conclusion, the TLPS material can be a promising candidate for a highly reliable conductive adhesive in power device packaging because remelting of the SAC305 solder, which is widely used in conventional power modules, is not observed.     

Enhanced Interfacial Stability of Hybrid‐Electrolyte Lithium‐Sulfur Batteries with a Layer of Multifunctional Polymer with Intrinsic Nanoporosity

The use of lithium‐ion conductive solid electrolytes offers a promising approach to address the polysulfide shuttle and the lithium‐dendrite problems in lithium‐sulfur (Li‐S) batteries. One critical issue with the development of solid‐electrolyte Li‐S batteries is the electrode–electrolyte interfaces. Herein, a strategic approach is presented by employing a thin layer of a polymer with intrinsic nanoporosity (PIN) on a Li⁺‐ion conductive solid electrolyte, which significantly enhances the ionic interfaces between the electrodes and the solid electrolyte. Among the various types of Li⁺‐ion solid electrolytes, NASICON‐type Li_1+xAl_xTi_2‐x(PO₄)₃ (LATP) offers advantages in terms of Li⁺‐ion conductivity, stability in ambient environment, and practical viability. However, LATP is susceptible to reaction with both the Li‐metal anode and polysulfides in Li‐S batteries due to the presence of easily reducible Ti⁴⁺ ions in it. The coating with a thin layer of PIN presented in this study overcomes the above issues. At the negative‐electrode side, the PIN layer prevents the direct contact of Li‐metal with the LATP solid electrolyte, circumventing the reduction of LATP by Li metal. At the positive electrode side, the PIN layer prevents the migration of polysulfides to the surface of LATP, preventing the reduction of LATP by polysulfides.     

Atomic Layer Deposition Inducing Integration of Co,N Codoped Carbon Sphere on 3D Foam with Hierarchically Porous Structures for Flexible Hydrogen Producing Device

Integration of metal–organic frameworks on deformation tolerant substrates exhibits a promising prospect in flexible electrode applications. A straightforward synthesis utilizing atomic layer deposition pretreating to induce the growth of a zeolitic imidazolate framework‐67 (ZIF‐67) layer on carbon foam (CF), which maintains high ZIF‐67 loading with a hierarchically porous structure and large surface area of 453 m² g^?1 is presented. With a subsequent pyrolysis process, three‐dimensional composite structures are obtained with Co, N codoped carbon spheres attached firmly on the CF framework, and CF bridges the individual carbon spheres to construct a conductive pathway. The composites are used as a flexible electrode for hydrogen production both in acid and alkaline electrolytes. The advances in the composite structure, such as the hierarchically porous structure, large surface area, and high loading of active material, lead to excellent electrochemical performance in terms of low overpotential of 142 mV and low Tafel slope of 73 mV dec^?1 in 0.5 m H₂SO₄. Most importantly, the composite structure with outstanding flexible property shows good catalytic performance under remarkable deformation, and after 100 repeated compression–recovery cycles, the performance degrades slightly. This work provides a new design of flexible electrode, which is promising for the hydrogen production industry.     

Building Artificial Solid‐Electrolyte Interphase with Uniform Intermolecular Ionic Bonds toward Dendrite‐Free Lithium Metal Anodes

Li metal has been widely regarded as a promising anode for next‐generation batteries due to its high theoretical capacity and low electrochemical potential. The unstable solid‐electrolyte interphase (SEI) and uncontrollable dendrite growth, however, incur severe safety hazards and hamper the practical application of Li metal anodes. Herein, an advanced artificial SEI layer constructed by [LiNBH]_n chains, which are crosslinked and self‐reinforced by their intermolecular Li? N ionic bonds, is designed to comprehensively stabilize Li metal anodes on a molecular level. Benefiting from its polymer‐like structure, the [LiNBH]_n layer is flexible and effectively tolerates the volume change of Li metal anodes. In addition, this layer with high polarity in its structure, helps to regulate the homogeneous distribution of the Li⁺ flux on Li electrodes via the further formation of Li? N bonds. The designed [LiNBH]_n layer is electrically nonconductive but highly ionically conductive, thus facilitating Li⁺ diffusion and confining Li deposition beneath the layer. Therefore, under the protection of the [LiNBH]_n layer, the Li metal anodes exhibit stable cycling at a 3 mA cm^?2 for more than 700 h, and the full cells with high lithium iron phosphate and sulfur cathodes mass loading also present excellent cycling stability.     

Large-Area Smooth Conductive Films Enabled by Scalable Slot-Die Coating of Ti3C2Tx MXene Aqueous Inks

Large-area flexible transparent conductive electrodes (TCEs) featuring excellent optoelectronic properties (low sheet resistance, R_s, at high transparency, T) are vital for integration in transparent wearable electronics (i.e., antennas, sensors, supercapacitors, etc.). Solution processing (i.e., printing and coating) of conductive inks yields highly uniform TCEs at low cost, holding great promise for commercially manufacturing of transparent electronics. However, to formulate such conductive inks as well as to realize continuous conductive films in the absence of percolation issue are quite challenging. Herein, the scalable slot-die coating of Ti₃C₂T_x MXene aqueous inks is reported for the first time to yield large-area uniform TCEs with outstanding optoelectronic performance, that is, average DC conductivity of 13 000 ± 500 S cm⁻¹. The conductive MXene nanosheets are forced to orientate horizontally as the inks are passing through the moving slot, leading to the rapid manufacturing of highly aligned MXene TCEs without notorious percolation problems. Moreover, through tuning the ink formulations, such conductive MXene films can be easily adjusted from transparent to opaque as required, demonstrating very low surface roughness and even mirror effects. These high-quality, slot-die-coated MXene TCEs also demonstrate excellent electrochemical charge storage properties when assembled into supercapacitors.