Reversibly Compressible Silanated Cellulose Nanofibril Aerogel for Triboelectric Taekwondo Scoring Sensors.

The integration of bio-based materials into triboelectric nanogenerators (TENGs) for energy harvesting from human body motions has sparked considerable research attention. Here, a silanated cellulose nanofibril (SCNF) aerogel is reported for structurally reliable TENGs and reversely compressible Taekwondo scoring sensors under repeated impacts. The preparation of the aerogel involves silanizing cellulose nanofibers (CNFs) with vinyltrimethoxysilane (VTMS), following by freeze-drying and post-heating treatment. The SCNF aerogel with crosslinked physico-chemical bonding and highly porous network is found to exhibit superior mechanical strength and reversible compressibility as well as enhanced water repellency and electron-donating ability. The TENG having a tribo-positive SCNF layer exhibits exceptional triboelectric performances, generating a voltage of 270 V, current of 11 µA, and power density of 401.1 mW m-2 under an applied force of 8 N at a frequency of 5 Hz. With its inherent merits in material composition, structural configuration, and device sensitivity, the SCNF TENG demonstrates the capability to seamlessly integrate into a Taekwondo protection gear, serving as an efficient self-powered sensor for monitoring hitting scores. This study highlights the significant potential of a facilely fabricated SCNF aerogel for the development of high-performance, bio-friendly, and cost-effective Bio-TENGs, enabling their application as self-powered wearable devices and sports engineering sensors.

Role of a cyclopentadienyl ligand in a heteroleptic alkoxide precursor in atomic layer deposition.

Alkoxide precursors have been highlighted for depositing carbon-free films, but their use in Atomic Layer Deposition (ALD) often exhibits a non-saturated growth. This indicates no self-limiting growth due to the chain reaction of hydrolysis or ligand decomposition caused by ß-hydride elimination. In the previous study, we demonstrated that self-limiting growth of ALD can be achieved using our newly developed precursor, hafnium cyclopentadienyl tris(N-ethoxy-2,2-dimethyl propanamido) [HfCp(edpa)3]. To elucidate the growth mechanism and the role of cyclopentadienyl (Cp) ligand in a heteroleptic alkoxide precursor, herein, we compare homoleptic and heteroleptic Hf precursors consisting of N-ethoxy-2,2-dimethyl propanamido (edpa) ligands with and without cyclopentadienyl ligand-hafnium tetrakis(N-ethoxy-2,2-dimethyl propanamido) [Hf(edpa)4] and HfCp(edpa)3. We also investigate the role of a Cp ligand in growth characteristics. By substituting an alkoxide ligand with a Cp ligand, we could modify the surface reaction during ALD, preventing undesired reactions. The last remaining edpa after Hf(edpa)4 adsorption can undergo a hydride elimination reaction, resulting in surface O-H generation. In contrast, Cp remains after the HfCp(edpa)3 adsorption. Accordingly, we observe proper ALD growth with self-limiting properties. Thus, a comparative study of different ligands of the precursors can provide critical clues to the design of alkoxide precursors for obtaining typical ALD growth with a saturation behavior.

Physicochemically Interlocked Sulfur Covalent Triazine Framework for Lithium-Sulfur Batteries with Exceptional Longevity.

An electronically conjugated functional triazine framework is used to synthesize a physicochemically interlocked sulfur cathode that delivers high energy density coupled with exceptional cycle life in lithium-sulfur batteries. Conventional melt-diffusion strategies to impregnate sulfur in the cathode offer poor cycle life due to physical mixing with weak interactions. By contrast, in this approach, sulfur is physicochemically entrapped within a nanoporous and heteroatom doped high surface area covalent triazine framework, resulting in outstanding electrochemical performance (≈89% capacity retention after 1000 cycles, the energy density of ≈2,022 Wh kg-1 sulfur and high-rate capability up to 12 C). The overall structural characteristics and interactions of sulfur with the covalent triazine framework are explored in detail to explain the intriguing properties of the sulfur cathode.

Magnetically and Electrically Responsive Soft Actuator Derived from Ferromagnetic Bimetallic Organic Framework.

The advancement in smart devices and soft robotics necessitates the use of multiresponsive soft actuators with high actuation stroke and stable reversibility for their use in real-world applications. Here, this work reports a magnetically and electrically dual responsive soft actuator based on neodymium and iron bimetallic organic frameworks (NdFeMOFs@700). The ferromagnetic NdFeMOFs@700 exhibits a porous carbon structure with excellent magnetization saturation (166.96 emu g-1 ) which allows its application to a dual functional material in both magnetoactive and electro-ionic actuations. The electro-ionic soft actuator, which is fabricated using NdFeMOFs@700 and PEDOT-PSS, demonstrates 4.5 times higher ionic charge storage capacity (68.21 mF cm-2 ) and has excellent cycle stability compared with the PEDOT-PSS based actuator. Under a low sinusoidal input voltage of 1 V, the dual-responsive actuator displays bending displacement of 15.46 mm and also generates deflection of 10 mm at 50 mT. Present results show that the ferromagnetic bimetallic organic frameworks can open a new way to make dual responsive soft actuators due to the hierarchically porous structures with its high redox activity, superior magnetic properties, and larger electrochemical capacitance. With the NdFeMOFs@700 based soft actuators, walking movement of a starfish robot is demonstrated by applying both the magnetic and electric fields.

Effective Approach for Fabricating Highly Precise High-Curvature Structural Patterns via Air-Bubble Induction.

Developing a new master mold-based patterning technology that can be used to accurately, precisely, and uniformly create large-area micropatterns while controlling the micropatterns of curved structures is essential for promoting innovative developments in various application fields. This study develops a new top-down lithographic process that can effectively produce structural patterns with high curvatures by growing isolated microbubbles in the master pattern holes. The isolated air-pocket lithography (IAL) we developed is based on the controlled behavior of micrometer-sized air pockets trapped between the grooves of the master pattern and the curable polymer. We successfully fabricated a concave array polydimethylsiloxane (PDMS) film and a convex array polymer film. In addition, the IAL mechanism was proven by confirming the expansion process of micrometer-sized air pockets trapped between the deep groove of the silicon master pattern and the PDMS coating film by using optical microscopy images. We successfully obtained complex three-dimensional structural patterns containing both 3D hollow spherical concave and ring-shaped two-dimensional convex patterns. This simple, fast, and effective high-curvature patterning technique is expected to provide innovative solutions for future applications such as nanoelectronics, optical devices, displays, and photovoltaics.

Unveiling the Effect of Superlattice Interfaces and Intermixing on Phase Change Memory Performance.

Superlattice (SL) phase change materials have shown promise to reduce the switching current and resistance drift of phase change memory (PCM). However, the effects of internal SL interfaces and intermixing on PCM performance remain unexplored, although these are essential to understand and ensure reliable memory operation. Here, using nanometer-thin layers of Ge2Sb2Te5 and Sb2Te3 in SL-PCM, we uncover that both switching current density (Jreset) and resistance drift coefficient (v) decrease as the SL period thickness is reduced (i.e., higher interface density); however, interface intermixing within the SL increases both. The signatures of distinct versus intermixed interfaces also show up in transmission electron microscopy, X-ray diffraction, and thermal conductivity measurements of our SL films. Combining the lessons learned, we simultaneously achieve low Jreset ≈ 3-4 MA/cm2 and ultralow v ≈ 0.002 in mushroom-cell SL-PCM with ∼110 nm bottom contact diameter, thus advancing SL-PCM technology for high-density storage and neuromorphic applications.

Elucidating the Reaction Mechanism of Atomic Layer Deposition of Al2O3 with a Series of Al(CH3)xCl3-x and Al(CyH2y+1)3 Precursors.

The adsorption of metalorganic and metal halide precursors on the SiO2 surface plays an essential role in thin-film deposition processes such as atomic layer deposition (ALD). In the case of aluminum oxide (Al2O3) films, the growth characteristics are influenced by the precursor structure, which controls both chemical reactivity and the geometrical constraints during deposition. In this work, a systematic study using a series of Al(CH3)xCl3-x (x = 0, 1, 2, and 3) and Al(CyH2y+1)3 (y = 1, 2, and 3) precursors is carried out using a combination of experimental spectroscopic techniques together with density functional theory calculations and Monte Carlo simulations to analyze differences across precursor molecules. Results show that reactivity and steric hindrance mutually influence the ALD surface reaction. The increase in the number of chlorine ligands in the precursor shifts the deposition temperature higher, an effect attributed to more favorable binding of the intermediate species due to higher Lewis acidity, while differences between precursors in film growth per cycle are shown to originate from variations in adsorption activation barriers and size-dependent saturation coverage. Comparison between the theoretical and experimental results indicates that the Al(CyH2y+1)3 precursors are favored to undergo two ligand exchange reactions upon adsorption at the surface, whereas only a single Cl-ligand exchange reaction is energetically favorable upon adsorption by the AlCl3 precursor. By pursuing the first-principles design of ALD precursors combined with experimental analysis of thin-film growth, this work enables a robust understanding of the effect of precursor chemistry on ALD processes.

Antagonistically Functionalized Diatom Biosilica for Bio-Triboelectric Generators.

Although biomaterial-based triboelectric nanogenerators (Bio-TENGs) for use in wearable electronics and implantable sensors have been developed, power generation is not suitable for satisfying the basic requirements for practical applications. Here, to greatly enhance output performances of Bio-TENG devices, an antagonistic approach of diatom frustules (DFs) with amine and fluorine chemical functionalizations is reported. The DFs are treated with piranha solution to increase the density of hydroxyl groups and tribo-positive and tribo-negative composite films are designed with antagonistically functionalized DFs. The tribo-positive composites having electron donating functionality consist of aminated DFs and cellulose nanocrystals (CNCs), while the tribo-negative composite is composed of fluorinated DFs and polydimethylsiloxane (PDMS). An antagonistically and chemically functionalized TENG (ACF TENG) with an efficient contact area of 9.6 cm2 under a force of 8 N and a frequency of 5 Hz exhibits an output voltage of 248 V, a short-circuit current of 16.4 µA, and a power density of 2.01 W m-2 , which is 16.6 times higher than a reference (CNC:PDMS) TENG. This study shows a simple antagonistic approach for chemical functionalization as an efficient method to manipulate the tribo-polarity of bio-additives for enhancing power generation of Bio-TENGs.

Self-Formation of Superhydrophobic Surfaces through Interfacial Energy Engineering between Liquids and Particles.

The superhydrophobic surface has been used in ultradry surface applications, such as the maritime industry, windshields, non-sticky surfaces, anti-icing surfaces, self-cleaning surfaces, and so forth. However, one of the main hurdles for the production of superhydrophobic surfaces is high-cost fabrication methods. Here, we report a handy process of self-synthesis fabrication of superhydrophobic surfaces with daily supplies. Driven by the physics of biscuit dunking, we introduce a method to self-synthesize superhydrophobic surfaces from daily supplies by coating a substrate with a liquid (liquids of paraffin from candles or polydimethylsiloxane) and subsequently sprinkling powders (food-desiccant silica, alumina, sugar, salt, or flour). A mechanistic study revealed that the capillary force, governed by surface energy difference, liquid viscosity, and powder pore size, draws the liquid solution into the porous channels within the powders. The entire surface of powders, in turn, is covered with the low-surface-energy liquid to maintain the porosity, creating a 3D porous nanostructure, resulting in a water contact angle over 160°. This work provides a scientific understanding that technological developments are closely related to the science that can be seen in our daily lives. Also, we believe that further intensive studies extended from this work could enable to home-fabricate a superhydrophobic surface, such as a bathtub and sink in bathrooms and a cooking area and sink in kitchens.

Ferrocene-Incorporated Cobalt Sulfide Nanoarchitecture for Superior Oxygen Evolution Reaction.

Here, ferrocene(Fc)-incorporated cobalt sulfide (Cox Sy ) nanostructures directly grown on carbon nanotube (CNT) or carbon fiber (CF) networks for electrochemical oxygen evolution reaction (OER) using a facile one-step solvothermal method are reported. The strong synergistic interaction between Fc-Cox Sy nanostructures and electrically conductive CNTs results in the superior electrocatalytic activity with a very small overpotential of ≈304 mV at 10 mA cm-2 and a low Tafel slope of 54.2 mV dec-1 in 1 m KOH electrolyte. Furthermore, the Fc-incorporated Cox Sy (FCoS) nanostructures are directly grown on the acid pretreated carbon fiber (ACF), and the resulting fabricated electrode delivers excellent OER performance with a low overpotential of ≈315 mV at 10 mA cm-2 . Such superior OER catalytic activity can be attributed to 3D Fc-Cox Sy nanoarchitectures that consist of a high concentration of vertical nanosheets with uniform distribution of nanoparticles that afford a large number of active surface areas and edge sites. Besides, the tight contact interface between ACF substrate and Fc-Cox Sy nanostructures could effectively facilitate the electron transfer rate in the OER. This study provides valuable insights for the rational design of energy storage and conversion materials by the incorporation of other transition metal into metal sulfide/oxide nanostructures utilizing metallocene.

Phenol-Derived Carbon Sealant Inspired by a Coalification Process.

Recently, emerging functions utilizing phenolic molecules, such as surface functionalizing agents or bioadhesives, have attracted significant interest. However, the most important role of phenolic compounds is to produce carbonized plant matter called "coal", which is widely used as an energy source in nearly all countries. Coalification is a long-term, high-temperature process in which phenols are converted into conducting carbonized matter. This study focuses on mimicking coalification processes to create conducting sealants from non-conducting phenolic compounds by heat treatment. We demonstrate that a phenolic adhesive, tri-hydroxybenzene (known as pyrogallol), and polyethylenimine mixture initially acts as an adhesive sealant that can be converted to a conducting carbon sealing material. The conductivity of the phenolic sealant is about 850 Ω-1 cm-1 , which is an approximately two-fold enhancement of the performance of carbon matter. Applications of the biomimetic adhesives described herein include conducting defect sealants in carbon nanomaterials and conducting binders for metal/carbon or ceramic/carbon composites.

An Electroactive and Transparent Haptic Interface Utilizing Soft Elastomer Actuators with Silver Nanowire Electrodes.

An electroactive and transparent haptic interface having a rectangular void pattern creates tunable surface textures by controlling the wavelength and amplitude of independent void-lines. To make an active tactile surface, the transparent haptic interface employs a silver nanowire (AgNW) electrode to be compliant with the deformed elastomer surface. Here, the dielectric elastomer is newly blended with polydimethylsiloxane and Ecoflex prepolymer to simultaneously control the mechanical stiffness and transparency. The relative resistance of the AgNW electrode on a single void line is nearly unchanged under bending test, confirming the high stretchability and conductivity of the nanowire-networked electrode. The optical transparencies are 92-85%, depending on the ratio of the Ecoflex solution. Transparency values decreas by 7 and 16% after coating with AgNWs at densities of 30 and 140 mg m-2 , respectively. Using EP31, the void line is deformed by 90 µm under a field intensity of 13.0 V µm-1 . The haptic surface is successfully controlled by applying voltage, which produces four different surface textures, from relatively smooth to rough feeling, depending on the distance between deformed void lines. This haptic interface can be applied to diverse display systems as an external add-on screen and will help to realize programmable surface textures in the future.

Microwave-Accelerated Rapid, Chemical Oxidant-Free, Material-Independent Surface Chemistry of Poly(dopamine).

A simple strategy for the rapid preparation of multifunctional polydopamine (pDA) coatings is demonstrated. Microwave irradiation of the coating solution enables the formation of a ≈18 nm thick, genuine pDA coating in 15 min, which is ≈18 times faster than conventional coating. The acceleration effect results from the radical generation and temperature increase, which facilitate thermally accelerated radical polymerization of dopamine.

Soft but Powerful Artificial Muscles Based on 3D Graphene-CNT-Ni Heteronanostructures.

Bioinspired soft ionic actuators, which exhibit large strain and high durability under low input voltages, are regarded as prospective candidates for future soft electronics. However, due to the intrinsic drawback of weak blocking force, the feasible applications of soft ionic actuators are limited until now. An electroactive artificial muscle electro-chemomechanically reinforced with 3D graphene-carbon nanotube-nickel heteronanostructures (G-CNT-Ni) to improve blocking force and bending deformation of the ionic actuators is demonstrated. The G-CNT-Ni heteronanostructure, which provides an electrically conductive 3D network and sufficient contact area with mobile ions in the polymer electrolyte, is embedded as a nanofiller in both ionic polymer and conductive electrodes of the ionic actuators. An ionic exchangeable composite membrane consisting of Nafion, G-CNT-Ni and ionic liquid (IL) shows improved tensile modulus and strength of up to 166% and 98%, respectively, and increased ionic conductivity of 0.254 S m-1 . The ionic actuator exhibits enhanced actuation performances including three times larger bending deformation, 2.37 times higher blocking force, and 4 h durability. The electroactive artificial muscle electro-chemomechanically reinforced with 3D G-CNT-Ni heteronanostructures offers improvements over current soft ionic actuator technologies and can advance the practical engineering applications.

Catalytic chemical vapor deposition of large-area uniform two-dimensional molybdenum disulfide using sodium chloride.

The effective synthesis of atomically thin molybdenum disulfides (MoS2) of high quality and uniformity over a large area is essential for their use in electronic and optical devices. In this work, we synthesize MoS2 that exhibit a high quality and large area uniformity using chemical vapor deposition (CVD) with volatile S organic compound and NaCl catalysts. In the latter process, the NaCl enhances the growth rate (5 min for synthesis of monolayer MoS2) and purity of the synthesized MoS2. The optical microscopy, Raman spectroscopy, x-ray photoemission spectroscopy, photoluminescence, and transmission electron microscopy measurements indicate that the NaCl-CVD MoS2 has a large grain size, clear Raman shift, strong photoluminescence, good stoichiometry, and 6-fold coordination symmetry. Moreover, we demonstrate that the electron mobility (10.4 cm2 V-1 s-1) and on/off current ratio (3 × 107) of monolayer MoS2 measured using a field-effect transistor are comparable to those of previously reported MoS2 synthesized using CVD.

Highly Flexible Hybrid CMOS Inverter Based on Si Nanomembrane and Molybdenum Disulfide.

2D semiconductor materials are being considered for next generation electronic device application such as thin-film transistors and complementary metal-oxide-semiconductor (CMOS) circuit due to their unique structural and superior electronics properties. Various approaches have already been taken to fabricate 2D complementary logics circuits. However, those CMOS devices mostly demonstrated based on exfoliated 2D materials show the performance of a single device. In this work, the design and fabrication of a complementary inverter is experimentally reported, based on a chemical vapor deposition MoS2 n-type transistor and a Si nanomembrane p-type transistor on the same substrate. The advantages offered by such CMOS configuration allow to fabricate large area wafer scale integration of high performance Si technology with transition-metal dichalcogenide materials. The fabricated hetero-CMOS inverters which are composed of two isolated transistors exhibit a novel high performance air-stable voltage transfer characteristic with different supply voltages, with a maximum voltage gain of ≈16, and sub-nano watt power consumption. Moreover, the logic gates have been integrated on a plastic substrate and displayed reliable electrical properties paving a realistic path for the fabrication of flexible/transparent CMOS circuits in 2D electronics.

An Electroactive, Tunable, and Frequency Selective Surface Utilizing Highly Stretchable Dielectric Elastomer Actuators Based on Functionally Antagonistic Aperture Control.

An active, frequency selective surface utilizing a silver-nanowire-coated dielectric elastomer with a butterfly-shaped aperture pattern is realized by properly exploiting the electroactive control of two antagonistic functions (stretching vs compression) on a patterned dielectric elastomer actuator.

A soft biomolecule actuator based on a highly functionalized bacterial cellulose nano-fiber network with carboxylic acid groups.

Upcoming human-related applications such as soft wearable electronics, flexible haptic systems, and active bio-medical devices will require bio-friendly actuating materials. Here, we report a soft biomolecule actuator based on carboxylated bacterial cellulose (CBC), ionic liquid (IL), and poly (3,4-ethylenedioxythiophene)-poly(styrenesulfonate) ( PEDOT: PSS) electrodes. Soft and biocompatible polymer-IL composites were prepared via doping of CBC with ILs. The highly conductive PEDOT: PSS layers were deposited on both sides of the CBC-IL membranes by a dip-coating technique to yield a sandwiched actuator system. Ionic conductivity and ionic exchange capacity of the CBC membrane can be increased up to 22.8 times and 1.5 times compared with pristine bacterial cellulose (BC), respectively, resulting in 8 times large bending deformation than the pure BC actuators with metallic electrodes in an open air environment. The developed CBC-IL actuators show significant progress in the development of biocompatible and soft actuating materials with quick response, low operating voltage and comparatively large bending deformation.

3D networked graphene-ferromagnetic hybrids for fast shape memory polymers with enhanced mechanical stiffness and thermal conductivity.

A novel 3D networked graphene-ferromagnetic hybrid can be easily fabricated using one-step microwave irradiation. By incorporating this hybrid material into shape memory polymers, the synergistic effects of fast speed and the enhancement of thermal conductivity and mechanical stiffness can be achieved. This can be broadly applicable to designing magneto-responsive shape memory polymers for multifunction applications.

Highly conductive, capacitive, flexible and soft electrodes based on a 3D graphene-nanotube-palladium hybrid and conducting polymer.

Highly conductive, capacitive and flexible electrodes are fabricated by employing 3D graphene-nanotube-palladium nanostructures and a PEDOT:PSS conducting polymer. The fabricated flexible electrodes, without any additional metallic current collectors, exhibit increased charge mobility and good mechanical properties; they also allow greater access to the electrolyte ions and hence are suitable for flexible energy storage applications.