Non-oxidized bare copper nanoparticles with surface excess electrons in air.

Copper (Cu) nanoparticles (NPs) have received extensive interest owing to their advantageous properties compared with their bulk counterparts. Although the natural oxidation of Cu NPs can be alleviated by passivating the surfaces with additional moieties, obtaining non-oxidized bare Cu NPs in air remains challenging. Here we report that bare Cu NPs with surface excess electrons retain their non-oxidized state over several months in ambient air. Cu NPs grown on an electride support with excellent electron transfer ability are encapsulated by the surface-accumulated excess electrons, exhibiting an ultralow work function of ~3.2 eV. Atomic-scale structural and chemical analyses confirm the absence of Cu oxide moiety at the outermost surface of air-exposed bare Cu NPs. Theoretical energetics clarify that the surface-accumulated excess electrons suppress the oxygen adsorption and consequently prohibit the infiltration of oxygen into the Cu lattice, provoking the endothermic reaction for oxidation process. Our results will further stimulate the practical use of metal NPs in versatile applications.

A Superior Method for Constructing Electrical Percolation Network of Nanocomposite Fibers: In Situ Thermally Reduced Silver Nanoparticles.

Nanocomposite fibers, composed of conductive nanoparticles and polymer matrix, are crucial for wearable electronics. However, the nanoparticle mixing approach results in aggregation and dispersion problems. A revolutionary synthesis method by premixing silver precursor ions (silver ammonium acetate) with polyvinyl alcohol is reported here. The solvation of ions-prevented aggregation, and uniformly distributed silver nanoparticles (in situ AgNPs, 77 nm) are formed after thermal reduction (155 °C) without using additional reducing or dispersion agents. The conductive fiber is synthesized by the wet spinning technology. After careful optimization, flower-shaped silver nanoparticles (AgNFs, 350-450 nm) are also employed as cofillers. The addition of in situ AgNPs (9.5 vol%) to AgNFs (30 vol%) increases electrical conductivity by 1434% (2090 to 32 064 S cm-1 ) through the efficient construction of percolation networks. The in situ AgNPs provide significantly higher conductivity compared with other secondary nanoparticle fillers. The gaseous byproducts dramatically increase flexibility with a moderate compromise in tensile strength (55 MPa). The particle-free ion-level uniform mixing of silver precursors, followed by in situ reduction, would be a fundamental paradigm shift in nanocomposite synthesis.

Silver Nanoflower Decorated Graphene Oxide Sponges for Highly Sensitive Variable Stiffness Stress Sensors.

Soft conductive materials should enable large deformation while keeping high electrical conductivity and elasticity. The graphene oxide (GO)-based sponge is a potential candidate to endow large deformation. However, it typically exhibits low conductivity and elasticity. Here, the highly conductive and elastic sponge composed of GO, flower-shaped silver nanoparticles (AgNFs), and polyimide (GO-AgNF-PI sponge) are demonstrated. The average pore size and porosity are 114 µm and 94.7%, respectively. Ag NFs have thin petals (8-20 nm) protruding out of the surface of a spherical bud (300-350 nm) significantly enhancing the specific surface area (2.83 m2 g-1 ). The electrical conductivity (0.306 S m-1 at 0% strain) of the GO-AgNF-PI sponge is increased by more than an order of magnitude with the addition of Ag NFs. A nearly perfect elasticity is obtained over a wide compressive strain range (0-90%). The strain-dependent, nonlinear variation of Young's modulus of the sponge provides a unique opportunity as a variable stiffness stress sensor that operates over a wide stress range (0-10 kPa) with a high maximum sensitivity (0.572 kPa-1 ). It allows grasping of a soft rose and a hard bottle, with the minimal object deformation, when attached on the finger of a robot gripper.

Laser patterning of highly conductive flexible circuits.

There has been considerable attention paid to highly conductive flexible adhesive (CFA) materials as electrodes and interconnectors for future flexible electronic devices. However, the patterning technology still needs to be developed to construct micro-scale electrodes and circuits. Here we developed the selective laser sintering technology where the pattering and curing were accomplished simultaneously without making additional masks. The CFA was composed of micro-scale Ag flakes, multiwalled carbon nanotubes decorated with Ag nanoparticles, and a nitrile-butadiene-rubber matrix. The Teflon-coated polyethylene terephthalate film was used as a flexible substrate. The width of lines (50-500 µm) and circuit patterns were controlled by the programmable scanning of a focused laser beam (power = 50 mW, scanning speed = 1 mm s-1). The laser irradiation removed solvent and induced effective coalescence among fillers providing a conductivity as high as 25 012 S cm-1. The conductivity stability was excellent under the ambient air and humid environments. The normalized resistance change of the pattern was smaller than 1.2 at the bending radius of 5 mm. The cyclability and adhesion of the laser-sintered line pattern on the substrate was excellent. A flexible circuit was fabricated sequentially for operating light emitting diodes during the bending motion, demonstrating excellent feasibility for practical applications in flexible electronics.

Extraordinarily high conductivity of flexible adhesive films by hybrids of silver nanoparticle-nanowires.

Highly conductive flexible adhesive (CFA) film was developed using micro-sized silver flakes (primary fillers), hybrids of silver nanoparticle-nanowires (secondary fillers) and nitrile butadiene rubber. The hybrids of silver nanoparticle-nanowires were synthesized by decorating silver nanowires with silver nanoparticle clusters using bifunctional cysteamine as a linker. The dispersion in ethanol was excellent for several months. Silver nanowires constructed electrical networks between the micro-scale silver flakes. The low-temperature surface sintering of silver nanoparticles enabled effective joining of silver nanowires to silver flakes. The hybrids of silver nanoparticle-nanowires provided a greater maximum conductivity (54 390 S cm(-1)) than pure silver nanowires, pure multiwalled carbon nanotubes, and multiwalled carbon nanotubes decorated with silver nanoparticles in nitrile butadiene rubber matrix. The resistance change was smallest upon bending when the hybrids of silver nanoparticle-nanowires were employed. The adhesion of the film on polyethylene terephthalate substrate was excellent. Light emitting diodes were successfully wired to the CFA circuit patterned by the screen printing method for application demonstration.

Silver nanowires decorated with silver nanoparticles for low-haze flexible transparent conductive films.

Silver nanowires have attracted much attention for use in flexible transparent conductive films (TCFs) due to their low sheet resistance and flexibility. However, the haze was too high for replacing indium-tin-oxide in high-quality display devices. Herein, we report flexible TCFs, which were prepared using a scalable bar-coating method, with a low sheet resistance (24.1 Ω/sq at 96.4% transmittance) and a haze (1.04%) that is comparable to that of indium-tin-oxide TCFs. To decrease the haze and maintain a low sheet resistance, small diameter silver nanowires (~20 nm) were functionalized with low-temperature surface-sintering silver nanoparticles (~5 nm) using bifunctional cysteamine. The silver nanowire-nanoparticle ink stability was excellent. The sheet resistance of the TCFs was decreased by 29.5% (from 34.2 to 24.1 Ω/sq) due to the functionalization at a low curing temperature of 85 °C. The TCFs were highly flexible and maintained their stability for more than 2 months and 10,000 bending cycles after coating with a protective layer.