Novel physical phenomena can emerge in low-dimensional nanomaterials. Bulk MoS2, a prototypical metal dichalcogenide, is an indirect bandgap semiconductor with negligible photoluminescence. When the ...MoS2 crystal is thinned to monolayer, however, a strong photoluminescence emerges, indicating an indirect to direct bandgap transition in this d-electron system. This observation shows that quantum confinement in layered d-electron materials like MoS2 provides new opportunities for engineering the electronic structure of matter at the nanoscale.
Controlling the bandstructure through local-strain engineering is an exciting avenue for tailoring optoelectronic properties of materials at the nanoscale. Atomically thin materials are particularly ...well-suited for this purpose because they can withstand extreme nonhomogeneous deformations before rupture. Here, we study the effect of large localized strain in the electronic bandstructure of atomically thin MoS2. Using photoluminescence imaging, we observe a strain-induced reduction of the direct bandgap and funneling of photogenerated excitons toward regions of higher strain. To understand these results, we develop a nonuniform tight-binding model to calculate the electronic properties of MoS2 nanolayers with complex and realistic local strain geometries, finding good agreement with our experimental results.
We report the structure of methylammonium lead(II) iodide perovskite in mesoporous TiO2, as used in high-performance solar cells. Pair distribution function analysis of X-ray scattering reveals a two ...component nanostructure: one component with medium range crystalline order (30 atom %) and another with only local structural coherence (70 atom %). The nanostructuring correlates with a blueshift of the absorption onset and increases the photoluminescence. Our findings underscore the importance of fully characterizing and controlling the structure for improved solar cell efficiency.
Planar supercapacitors have recently attracted much attention owing to their unique and advantageous design for 2D nanomaterials based energy storage devices. However, improving the electrochemical ...performance of planar supercapacitors still remains a great challenge. Here we report for the first time a novel, high-performance in-plane supercapacitor based on hybrid nanostructures of quasi-2D ultrathin MnO2/graphene nanosheets. Specifically, the planar structures based on the δ-MnO2 nanosheets integrated on graphene sheets not only introduce more electrochemically active surfaces for absorption/desorption of electrolyte ions, but also bring additional interfaces at the hybridized interlayer areas to facilitate charge transport during charging/discharging processes. The unique structural design for planar supercapacitors enables great performance enhancements compared to graphene-only devices, exhibiting high specific capacitances of 267 F/g at current density of 0.2 A/g and 208 F/g at 10 A/g and excellent rate capability and cycling stability with capacitance retention of 92% after 7000 charge/discharge cycles. Moreover, the high planar malleability of planar supercapacitors makes possible superior flexibility and robust cyclability, yielding capacitance retention over 90% after 1000 times of folding/unfolding. Ultrathin 2D nanomaterials represent a promising material platform to realize highly flexible planar energy storage devices as the power back-ups for stretchable/flexible electronic devices.
Lithium sulfur batteries have brought significant advancement to the current state-of-art battery technologies because of their high theoretical specific energy, but their wide-scale implementation ...has been impeded by a series of challenges, especially the dissolution of intermediate polysulfides species into the electrolyte. Conductive polymers in combination with nanostructured sulfur have attracted great interest as promising matrices for the confinement of lithium polysulfides. However, the roles of different conductive polymers on the electrochemical performances of sulfur electrode remain elusive and poorly understood due to the vastly different structural configurations of conductive polymer–sulfur composites employed in previous studies. In this work, we systematically investigate the influence of different conductive polymers on the sulfur cathode based on conductive polymer-coated hollow sulfur nanospheres with high uniformity. Three of the most well-known conductive polymers, polyaniline (PANI), polypyrrole (PPY), and poly(3,4-ethylenedioxythiophene) (PEDOT), were coated, respectively, onto monodisperse hollow sulfur nanopsheres through a facile, versatile, and scalable polymerization process. The sulfur cathodes made from these well-defined sulfur nanoparticles act as ideal platforms to study and compare how coating thickness, chemical bonding, and the conductivity of the polymers affected the sulfur cathode performances from both experimental observations and theoretical simulations. We found that the capability of these three polymers in improving long-term cycling stability and high-rate performance of the sulfur cathode decreased in the order of PEDOT > PPY > PANI. High specific capacities and excellent cycle life were demonstrated for sulfur cathodes made from these conductive polymer-coated hollow sulfur nanospheres.
Graphene is highly desirable as an electromagnetic wave (EM) absorber because of its large interface, high dielectric loss, and low density. Nevertheless, the conductive and electromagnetic ...parameters of pure graphene are too high to meet the requirement of impedance match, which results in strong reflection and weak absorption. In this paper, we report a facile solvothermal route to synthesize reduced graphene oxide (RGO) nanosheets combined with surface-modified γ-Fe2O3 colloidal nanoparticle clusters. The obtained two-dimensional hybrids exhibit a relatively low EM reflection coefficient (RC) and wide effective absorption bandwidth, which are mainly attributed to the unique microstructure of colloidal nanoparticle clusters assembled on RGO. The nanoparticle clusters have more interfaces. The interfacial polarization within nanoparticle clusters and conductivity loss of RGO plays an important role in absorbing EM power. The minimum RC reaches −59.65 dB at 10.09 GHz with a matching thickness of 2.5 mm. The special integration of some metal oxide semiconductor crystals assembled on RGO sheets provides an effective avenue to design metal oxide semiconductor/carbon hybrids as EM absorbing materials.
Artificial photosynthesis, the biomimetic approach to converting sunlight’s energy directly into chemical fuels, aims to imitate nature by using an integrated system of nanostructures, each of which ...plays a specific role in the sunlight-to-fuel conversion process. Here we describe a fully integrated system of nanoscale photoelectrodes assembled from inorganic nanowires for direct solar water splitting. Similar to the photosynthetic system in a chloroplast, the artificial photosynthetic system comprises two semiconductor light absorbers with large surface area, an interfacial layer for charge transport, and spatially separated cocatalysts to facilitate the water reduction and oxidation. Under simulated sunlight, a 0.12% solar-to-fuel conversion efficiency is achieved, which is comparable to that of natural photosynthesis. The result demonstrates the possibility of integrating material components into a functional system that mimics the nanoscopic integration in chloroplasts. It also provides a conceptual blueprint of modular design that allows incorporation of newly discovered components for improved performance.
We discovered for the first time that light can twist metal to control the chirality of metal nanostructures (hereafter, chiral metal nanoneedles). The helicity of optical vortices is transferred to ...the constituent elements of the irradiated material (mostly melted material), resulting in the formation of chiral metal nanoneedles. The chirality of these nanoneedles could be controlled by just changing the sign of the helicity of the optical vortex. The tip curvature of these chiral nanoneedles was measured to be <40 nm, which is less than 1/25th of the laser wavelength (1064 nm). Such chiral metal nanoneedles will enable us to selectively distinguish the chirality and optical activity of molecules and chemical composites on a nanoscale and they will provide chiral selectivity for nanoscale imaging systems (e.g., atomic force microscopes), chemical reactions on plasmonic nanostructures, and planar metamaterials.
Plasmonic nanostructures enable the generation of large electromagnetic fields confined to small volumes, potentially providing a route for the development of nanoengineered nonlinear optical media. ...A metal-capped hemispherical nanoparticle, also known as a nanocup, generates second harmonic light with increasing intensity as the angle between the incident fundamental beam and the nanocup symmetry axis is increased. Nanoparticle orientation also modifies the emission direction of the second harmonic light. With conversion efficiencies similar to those of inorganic SHG crystals, these structures provide a promising approach for the design and fabrication of stable, synthetic second-order nonlinear optical materials tailored for specific wavelengths.
Individual monolayers of metal dichalcogenides are atomically thin two-dimensional crystals with attractive physical properties different from those of their bulk counterparts. Here we describe the ...direct synthesis of WS2 monolayers with triangular morphologies and strong room-temperature photoluminescence (PL). The Raman response as well as the luminescence as a function of the number of S–W–S layers is also reported. The PL weakens with increasing number of layers due to a transition from direct band gap in a monolayer to indirect gap in multilayers. The edges of WS2 monolayers exhibit PL signals with extraordinary intensity, around 25 times stronger than that at the platelet’s center. The structure and chemical composition of the platelet edges appear to be critical for PL enhancement.
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