Graphene and its composites are widely investigated as supercapacitor electrodes due to their large specific surface area. However, the severe aggregation and disordered alignment of graphene sheets hamper the maximum utilization of its surface area. Here we report an optimized structure for supercapacitor electrode, i.e., the vertical graphene sheets, which have a vertical structure and open architecture for ion transport pathway. The effect of morphology and orientation of vertical graphene on the performance of supercapacitor is examined using a combination of model calculation and experimental study. Both results consistently demonstrate that the vertical graphene electrode has a much superior performance than that of lateral graphene electrode. Typically, the areal capacitances of a vertical graphene electrode reach 8.4 mF/cm(2) at scan rate of 100 mV/s; this is about 38% higher than that of a lateral graphene electrode and about 6 times higher than that of graphite paper. To further improve its performance, a MnO2 nanoflake layer is coated on the surface of graphene to provide a high pseudocapacitive contribution to the overall areal capacitance which increases to 500 mF/cm(2) at scan rate of 5 mV/s. The reasons for these significant improvements are studied in detail and are attributed to the fast ion diffusion and enhanced charge storage capacity. The microscopic manipulation of graphene electrode configuration could greatly improve its specific capacitance, and furthermore, boost the energy density of supercapacitor. Our results demonstrate that the vertical graphene electrode is more efficient and practical for the high performance energy storage device with high power and energy densities.
Compared with conventional rigid devices, the elastic substrates integrated with functional components offer various advantages, such as flexibility, dynamic tunability, and biocompatibility. However, the reliable formations of 2D nanoparticles, nanogaps, and 3D nanostructures on elastic substrates are still challenging. The conventional transfer method plays an important role in the fabrication of microstructures on elastic substrates; however, it could not fabricate structures with feature size less than a few micrometers. In this article, we have developed a flexible technique based on the "metal-assisted transfer" strategy. The key concept is to introduce a metal film as an assistant layer between nanostructures and silicon substrates to help the fabrication of nanostructures which cannot be successfully transferred in the conventional transfer method. Various 2D nanostructures, which are difficult to achieve on elastic substrates, could be reliably defined using this approach. The desired gap distances and even sub-10 nm metal gaps between adjacent nanoparticles can be controllably achieved. Moreover, 3D nanostructures can be directly assembled from the prestrained 2D precursors based on the developed technique. Comparing with the previous reports, our fabrication method contains only a one-step transfer process without selective bonding or a second transfer process. Significantly, the 3D nanostructures presented here are 2 orders of magnitude smaller than the state-of-the-art mechanically assembled 3D structures in unit cell size. The proposed method may become a mainstream technology for the nano-optics and ultracompact optoelectronic devices due to its multifunctionalities and superior advantages in achieving tunable nanoparticles as well as 3D nanostructures.
Plasmonic nanostructures offer an enticing prospect in many applications, ranging from lasing to biosensing, due to their unrivaled light concentration beyond the diffraction limit. However, this promise is substantially undercut by the intrinsically high losses in metals. Here, an experimental ultra‐high‐Q plasmon resonance with a linewidth down to 2 nm (Q‐factor ≈ 350) and a resonance intensity of 51% in an ultrasmooth gold nanogroove array is reported. Such an experimental ultranarrow resonance arises from two key factors. First, a geometrical‐induced coupling between the Fabry–Pérot and Wood's anomaly modes significantly suppresses the groove array's radiative damping. Second, an ultrasmooth gold surface fabricated by template stripping minimizes its surface scattering and grain boundary scattering. Benefiting from this ultranarrow resonance, a figure of merit (FOM) of 284 and an FOM* of 617 in refraction index (RI) sensing under normally incident detection are demonstrated, the former of which is the record FOM in all reported broad‐RI‐range plasmonic RI sensors. The array is further demonstrated as a surface thickness sensor for detecting mercaptocarboxylic acids with the surface sensitivity of 0.18 nm/CH2, which suggests that the array is a promising platform for thickness detection of surface analytes and label‐free biomedical sensing.
High-performance strain sensors, composed of various artificial sensing materials on/in stretchable substrates, show great promise for applications in flexible electronic devices. Here, we demonstrated a highly sensitive and durable strain sensor consisting of a ribbon of close-packed sea-urchin-shaped silver nanoparticles (SUSNs) sandwiched between two layers of poly(dimethylsiloxane) (PDMS). Each of SUSNs possesses highdensity and spherically distributed sharp spines over the body, which promotes electron transduction and further improves signal detection. This SUSN-based sensor possesses a desirable integration of high sensitivity (a gauge factor of 60) and large stretchability (up to 25%) at tensile sensing, broadening its application in wearable devices. Moreover, it also shows fast response (48 ms), good reproducibility, and long-term stability (>2500 cycles at 20% strain). It can also be used to detect compressing (sensitivity up to 31.5) and folding-type bending deformations. The sensing mechanism, the resistance of the sensors varying as the deformation load, results from the inter-spine contacts change and the microcracks evolution caused by variation in the gap between SUSNs. The sensor's sensitivity at different degrees of strain was also achieved by controlling the width of the closepacked SUSNs ribbon. For practical demonstration, the SUSN-based sensors could be used as wearable devices for monitoring human activities ranging from subtle deformations to substantial movements.
One of the most fascinating and important merits of graphene plasmonics is their tunability over a wide range. While chemical doping has proven to be a facile and effective way to create graphene plasmons, most of the previous studies focused on the macroscopic behaviors of the plasmons in chemically-doped graphene and little was known about their nanoscale responses and related mechanisms. Here, to the best of our knowledge, we present the first experimental near-field optical study on chemically-doped graphene with improved surface plasmon characteristics. By using a scattering-type scanning near-field optical microscope (s-SNOM), we managed to show that the graphene plasmons can be tuned and improved using a facile chemical doping method. Specifically, the plasmon interference patterns near the edge of the monolayer graphene were substantially enhanced via nitric acid (HNO3) exposure. The plasmon-related characteristics can be deduced by analyzing such plasmonic fringes, which exhibited a longer plasmon wavelength and reduced plasmon damping rate. In addition, the local carrier density and therefore the Fermi energy level (EF) of graphene can be obtained from the plasmonic nano-imaging, which indicated that the enhanced plasmon oscillation originated from the injection of free holes into graphene by HNO3. These findings were further corroborated by theoretical calculations using density functional theory (DFT). We believe that our findings provide a clear nanoscale picture on improving graphene plasmonics by chemical doping, which will be helpful for optimizing graphene plasmonics and for elucidating the mechanisms of two-dimensional light confinement by atomically thick materials.
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