Showing papers in "ACS Nano in 2013"
Ohio State University1, Stanford University2, North Carolina State University3, Pennsylvania State University4, Columbia University5, Northwestern University6, University of Texas at Austin7, University of Notre Dame8, Cornell University9, University of California, Berkeley10, Case Western Reserve University11
TL;DR: The properties and advantages of single-, few-, and many-layer 2D materials in field-effect transistors, spin- and valley-tronics, thermoelectrics, and topological insulators, among many other applications are highlighted.
Abstract: Graphene’s success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in...
4,123 citations
TL;DR: This paper reviews the fundamentals of the TENG in the three basic operation modes: vertical contact-separation mode, in-plane sliding mode, and single-electrode mode and predicts that a better enhancement of the output power density will be achieved in the next few years.
Abstract: Triboelectrification is an effect that is known to each and every one probably since ancient Greek time, but it is usually taken as a negative effect and is avoided in many technologies. We have recently invented a triboelectric nanogenerator (TENG) that is used to convert mechanical energy into electricity by a conjunction of triboelectrification and electrostatic induction. As for this power generation unit, in the inner circuit, a potential is created by the triboelectric effect due to the charge transfer between two thin organic/inorganic films that exhibit opposite tribo-polarity; in the outer circuit, electrons are driven to flow between two electrodes attached on the back sides of the films in order to balance the potential. Since the most useful materials for TENG are organic, it is also named organic nanogenerator, which is the first using organic materials for harvesting mechanical energy. In this paper, we review the fundamentals of the TENG in the three basic operation modes: vertical contact-...
2,102 citations
TL;DR: In this paper, the authors report differential reflectance and PL spectra of mono-to-few-layer Molybdenum disulfide (MoS2) and WSe2 that indicate that the band structure of these materials undergoes similar indirect-todirect gap transition when thinned to a single monolayer.
Abstract: Geometrical confinement effect in exfoliated sheets of layered materials leads to significant evolution of energy dispersion in mono- to few-layer thickness regime. Molybdenum disulfide (MoS2) was recently found to exhibit indirect-to-direct gap transition when the thickness is reduced to a single monolayer. Emerging photoluminescence (PL) from monolayer MoS2 opens up opportunities for a range of novel optoelectronic applications of the material. Here we report differential reflectance and PL spectra of mono- to few-layer WS2 and WSe2 that indicate that the band structure of these materials undergoes similar indirect-to-direct gap transition when thinned to a single monolayer. The transition is evidenced by distinctly enhanced PL peak centered at 630 and 750 nm in monolayer WS2 and WSe2, respectively. Few-layer flakes are found to exhibit comparatively strong indirect gap emission along with direct gap hot electron emission, suggesting high quality of synthetic crystals prepared by a chemical vapor transp...
1,726 citations
TL;DR: This research might provide a method for flexible, lightweight, high-performance, low-cost, and environmentally friendly materials used in energy conversion and storage systems for the effective use of renewable energy.
Abstract: A lightweight, flexible, and highly efficient energy management strategy is needed for flexible energy-storage devices to meet a rapidly growing demand. Graphene-based flexible supercapacitors are one of the most promising candidates because of their intriguing features. In this report, we describe the use of freestanding, lightweight (0.75 mg/cm2), ultrathin (<200 μm), highly conductive (55 S/cm), and flexible three-dimensional (3D) graphene networks, loaded with MnO2 by electrodeposition, as the electrodes of a flexible supercapacitor. It was found that the 3D graphene networks showed an ideal supporter for active materials and permitted a large MnO2 mass loading of 9.8 mg/cm2 (∼92.9% of the mass of the entire electrode), leading to a high area capacitance of 1.42 F/cm2 at a scan rate of 2 mV/s. With a view to practical applications, we have further optimized the MnO2 content with respect to the entire electrode and achieved a maximum specific capacitance of 130 F/g. In addition, we have also explored t...
1,309 citations
TL;DR: The results show that, compared to the single-layer counterpart, transistors of few MoS2 layers exhibit excellent sensitivity, recovery, and ability to be manipulated by gate bias and green light, and ab initio DFT calculations show that the charge transfer is the reason for the decrease in resistance in the presence of applied field.
Abstract: Most of recent research on layered chalcogenides is understandably focused on single atomic layers. However, it is unclear if single-layer units are the most ideal structures for enhanced gas–solid interactions. To probe this issue further, we have prepared large-area MoS2 sheets ranging from single to multiple layers on 300 nm SiO2/Si substrates using the micromechanical exfoliation method. The thickness and layering of the sheets were identified by optical microscope, invoking recently reported specific optical color contrast, and further confirmed by AFM and Raman spectroscopy. The MoS2 transistors with different thicknesses were assessed for gas-sensing performances with exposure to NO2, NH3, and humidity in different conditions such as gate bias and light irradiation. The results show that, compared to the single-layer counterpart, transistors of few MoS2 layers exhibit excellent sensitivity, recovery, and ability to be manipulated by gate bias and green light. Further, our ab initio DFT calculations...
1,126 citations
TL;DR: Solar illumination of broadly absorbing metal or carbon nanoparticles dispersed in a liquid produces vapor without the requirement of heating the fluid volume, enabling important compact solar applications such as sterilization of waste and surgical instruments in resource-poor locations.
Abstract: Solar illumination of broadly absorbing metal or carbon nanoparticles dispersed in a liquid produces vapor without the requirement of heating the fluid volume. When particles are dispersed in water at ambient temperature, energy is directed primarily to vaporization of water into steam, with a much smaller fraction resulting in heating of the fluid. Sunlight-illuminated particles can also drive H2O–ethanol distillation, yielding fractions significantly richer in ethanol content than simple thermal distillation. These phenomena can also enable important compact solar applications such as sterilization of waste and surgical instruments in resource-poor locations.
1,082 citations
TL;DR: The exploration of a three-dimensional (3D) graphene hydrogel for the fabrication of high-performance solid-state flexible supercapacitors demonstrates the exciting potential of 3D graphene macrostructures for high- performance flexible energy storage devices.
Abstract: Flexible solid-state supercapacitors are of considerable interest as mobile power supply for future flexible electronics. Graphene or carbon nanotubes based thin films have been used to fabricate flexible solid-state supercapacitors with high gravimetric specific capacitances (80–200 F/g), but usually with a rather low overall or areal specific capacitance (3–50 mF/cm2) due to the ultrasmall electrode thickness (typically a few micrometers) and ultralow mass loading, which is not desirable for practical applications. Here we report the exploration of a three-dimensional (3D) graphene hydrogel for the fabrication of high-performance solid-state flexible supercapacitors. With a highly interconnected 3D network structure, graphene hydrogel exhibits exceptional electrical conductivity and mechanical robustness to make it an excellent material for flexible energy storage devices. Our studies demonstrate that flexible supercapacitors with a 120 μm thick graphene hydrogel thin film can exhibit excellent capaciti...
1,026 citations
TL;DR: It is demonstrated theoretically and experimentally that the interference of electric and magnetic optically induced modes in individual subwavelength silicon nanodisks can lead to the suppression of resonant backscattering and to enhanced resonant forward scattering of light.
Abstract: Interference of optically induced electric and magnetic modes in high-index all-dielectric nanoparticles offers unique opportunities for tailoring directional scattering and engineering the flow of light. In this article we demonstrate theoretically and experimentally that the interference of electric and magnetic optically induced modes in individual subwavelength silicon nanodisks can lead to the suppression of resonant backscattering and to enhanced resonant forward scattering of light. To this end we spectrally tune the nanodisk’s fundamental electric and magnetic resonances with respect to each other by a variation of the nanodisk aspect ratio. This ability to tune two modes of different character within the same nanoparticle provides direct control over their interference, and, in consequence, allows for engineering the particle’s resonant and off-resonant scattering patterns. Most importantly, measured and numerically calculated transmittance spectra reveal that backward scattering can be suppresse...
1,021 citations
TL;DR: This work demonstrates field-effect transistors with MoS2 channels, hBN dielectric, and graphene gate electrodes, and takes advantage of the mechanical strength and flexibility of these materials to create flexible and transparent FETs that show unchanged performance up to 1.5% strain.
Abstract: Atomically thin forms of layered materials, such as conducting graphene, insulating hexagonal boron nitride (hBN), and semiconducting molybdenum disulfide (MoS2), have generated great interests recently due to the possibility of combining diverse atomic layers by mechanical “stacking” to create novel materials and devices. In this work, we demonstrate field-effect transistors (FETs) with MoS2 channels, hBN dielectric, and graphene gate electrodes. These devices show field-effect mobilities of up to 45 cm2/Vs and operating gate voltage below 10 V, with greatly reduced hysteresis. Taking advantage of the mechanical strength and flexibility of these materials, we demonstrate integration onto a polymer substrate to create flexible and transparent FETs that show unchanged performance up to 1.5% strain. These heterostructure devices consisting of ultrathin two-dimensional (2D) materials open up a new route toward high-performance flexible and transparent electronics.
1,004 citations
TL;DR: Nanoporous nickel hydroxide thin film was grown on the surface of ultrathin-graphite foam (UGF) via a hydrothermal reaction and used as the electrode in a supercapacitor without the need for addition of either binder or metal-based current collector.
Abstract: Nanoporous nickel hydroxide (Ni(OH)2) thin film was grown on the surface of ultrathin-graphite foam (UGF) via a hydrothermal reaction. The resulting free-standing Ni(OH)2/UGF composite was used as the electrode in a supercapacitor without the need for addition of either binder or metal-based current collector. The highly conductive 3D UGF network facilitates electron transport and the porous Ni(OH)2 thin film structure shortens ion diffusion paths and facilitates the rapid migration of electrolyte ions. An asymmetric supercapacitor was also made and studied with Ni(OH)2/UGF as the positive electrode and activated microwave exfoliated graphite oxide (‘a-MEGO’) as the negative electrode. The highest power density of the fully packaged asymmetric cell (44.0 kW/kg) was much higher (2–27 times higher), while the energy density was comparable to or higher, than high-end commercially available supercapacitors. This asymmetric supercapacitor had a capacitance retention of 63.2% after 10 000 cycles.
992 citations
TL;DR: A facile and scalable in situ synthesis strategy is developed to fabricate carbon-encapsulated Fe3O4 nanoparticles homogeneously embedded in two-dimensional (2D) porous graphitic carbon nanosheets as a durable high-rate lithium ion battery anode material.
Abstract: A facile and scalable in situ synthesis strategy is developed to fabricate carbon-encapsulated Fe3O4 nanoparticles homogeneously embedded in two-dimensional (2D) porous graphitic carbon nanosheets (Fe3O4@C@PGC nanosheets) as a durable high-rate lithium ion battery anode material. With assistance of the surface of NaCl particles, 2D Fe@C@PGC nanosheets can be in situ synthesized by using the Fe(NO3)3·9H2O and C6H12O6 as the metal and carbon precursor, respectively. After annealing under air, the Fe@C@PGC nanosheets can be converted to Fe3O4@C@PGC nanosheets, in which Fe3O4 nanoparticles (∼18.2 nm) coated with conformal and thin onion-like carbon shells are homogeneously embedded in 2D high-conducting carbon nanosheets with a thickness of less than 30 nm. In the constructed architecture, the thin carbon shells can avoid the direct exposure of encapsulated Fe3O4 to the electrolyte and preserve the structural and interfacial stabilization of Fe3O4 nanoparticles. Meanwhile, the flexible and conductive PGC nano...
TL;DR: This material represents a new class of covalently terminated graphane analogues and has great potential for a wide range of optoelectronic and sensing applications, especially since theory predicts a direct band gap of 1.53 eV and an electron mobility ca.
Abstract: Graphene’s success has shown not only that it is possible to create stable, single-atom-thick sheets from a crystalline solid but that these materials have fundamentally different properties than the parent material. We have synthesized for the first time, millimeter-scale crystals of a hydrogen-terminated germanium multilayered graphane analogue (germanane, GeH) from the topochemical deintercalation of CaGe2. This layered van der Waals solid is analogous to multilayered graphane (CH). The surface layer of GeH only slowly oxidizes in air over the span of 5 months, while the underlying layers are resilient to oxidation based on X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy measurements. The GeH is thermally stable up to 75 °C; however, above this temperature amorphization and dehydrogenation begin to occur. These sheets can be mechanically exfoliated as single and few layers onto SiO2/Si surfaces. This material represents a new class of covalently terminated graphane analogue...
TL;DR: In this article, the authors combine the unique electronic properties of semiconducting monolayer MoS2 with the high conductivity of graphene to build a 2D heterostructure capable of information storage.
Abstract: Memory cells are an important building block of digital electronics We combine here the unique electronic properties of semiconducting monolayer MoS2 with the high conductivity of graphene to build a 2D heterostructure capable of information storage MoS2 acts as a channel in an intimate contact with graphene electrodes in a field-effect transistor geometry Our prototypical all-2D transistor is further integrated with a multilayer graphene charge trapping layer into a device that can be operated as a nonvolatile memory cell Because of its band gap and 2D nature, monolayer MoS2 is highly sensitive to the presence of charges in the charge trapping layer, resulting in a factor of 10(4) difference between memory program and erase states The two-dimensional nature of both the contact and the channel can be harnessed for the fabrication of flexible nanoelectronic devices with large-scale integration
TL;DR: Employing high-yield production of layered materials by liquid-phase exfoliation, molybdenum disulfide (MoS2) dispersions with large populations of single and few layers were prepared and exhibited significant saturable absorption (SA) for the femtosecond pulses.
Abstract: Employing high-yield production of layered materials by liquid-phase exfoliation, molybdenum disulfide (MoS2) dispersions with large populations of single and few layers were prepared. Electron microscopy verified the high quality of the two-dimensional MoS2 nanostructures. Atomic force microscopy analysis revealed that ∼39% of the MoS2 flakes had thicknesses of less than 5 nm. Linewidth and frequency difference of the E12g and A1g Raman modes confirmed the effective reduction of flake thicknesses from the bulk MoS2 to the dispersions. Ultrafast nonlinear optical (NLO) properties were investigated using an open-aperture Z-scan technique. All experiments were performed using 100 fs pulses at 800 nm from a mode-locked Ti:sapphire laser. The MoS2 nanosheets exhibited significant saturable absorption (SA) for the femtosecond pulses, resulting in the third-order NLO susceptibility Imχ(3) ∼ 10–15 esu, figure of merit ∼10–15 esu cm, and free-carrier absorption cross section ∼10–17 cm2. Induced free carrier densi...
TL;DR: These exquisite carbons were able to be achieved by simple hydrothermal carbonization combined with activation by taking advantage of the complex multilayered structure of a hemp bast fiber precursor, providing among the best power-energy characteristics ever reported for an electrochemical capacitor.
Abstract: We created unique interconnected partially graphitic carbon nanosheets (10–30 nm in thickness) with high specific surface area (up to 2287 m2 g–1), significant volume fraction of mesoporosity (up to 58%), and good electrical conductivity (211–226 S m–1) from hemp bast fiber. The nanosheets are ideally suited for low (down to 0 °C) through high (100 °C) temperature ionic-liquid-based supercapacitor applications: At 0 °C and a current density of 10 A g–1, the electrode maintains a remarkable capacitance of 106 F g–1. At 20, 60, and 100 °C and an extreme current density of 100 A g–1, there is excellent capacitance retention (72–92%) with the specific capacitances being 113, 144, and 142 F g–1, respectively. These characteristics favorably place the materials on a Ragone chart providing among the best power–energy characteristics (on an active mass normalized basis) ever reported for an electrochemical capacitor: At a very high power density of 20 kW kg–1 and 20, 60, and 100 °C, the energy densities are 19, 3...
TL;DR: Analysis of the current-voltage (J-V) characteristics at various light intensities provides information on the different recombination mechanisms in the BHJ solar cells with different thicknesses of the Ca layer, revealing that the J-V curves are dominated by first-order recombination from the short-circuit condition to the maximum power point and evolve to bimolecular recombination in the range of voltage in the optimized device with a Ca thickness of 20 nm.
Abstract: Solution-processed small-molecule p-DTS(FBTTh2)2:PC71BM bulk heterojunction (BHJ) solar cells with power conversion efficiency of 8.01% are demonstrated. The fill factor (FF) is sensitive to the thickness of a calcium layer between the BHJ layer and the Al cathode; for 20 nm Ca thickness, the FF is 73%, the highest value reported for an organic solar cell. The maximum external quantum efficiency exceeds 80%. After correcting for the total absorption in the cell through normal incidence reflectance measurements, the internal quantum efficiency approaches 100% in the spectral range of 600–650 nm and well over 80% across the entire spectral range from 400 to 700 nm. Analysis of the current–voltage (J–V) characteristics at various light intensities provides information on the different recombination mechanisms in the BHJ solar cells with different thicknesses of the Ca layer. Our analysis reveals that the J–V curves are dominated by first-order recombination from the short-circuit condition to the maximum pow...
TL;DR: It is demonstrated that peat moss, a wild plant that covers 3% of the earth's surface, serves as an ideal precursor to create sodium ion battery anodes with some of the most attractive electrochemical properties ever reported for carbonaceous materials.
Abstract: We demonstrate that peat moss, a wild plant that covers 3% of the earth’s surface, serves as an ideal precursor to create sodium ion battery (NIB) anodes with some of the most attractive electrochemical properties ever reported for carbonaceous materials. By inheriting the unique cellular structure of peat moss leaves, the resultant materials are composed of three-dimensional macroporous interconnected networks of carbon nanosheets (as thin as 60 nm). The peat moss tissue is highly cross-linked, being rich in lignin and hemicellulose, suppressing the nucleation of equilibrium graphite even at 1100 °C. Rather, the carbons form highly ordered pseudographitic arrays with substantially larger intergraphene spacing (0.388 nm) than graphite (c/2 = 0.3354 nm). XRD analysis demonstrates that this allows for significant Na intercalation to occur even below 0.2 V vs Na/Na+. By also incorporating a mild (300 °C) air activation step, we introduce hierarchical micro- and mesoporosity that tremendously improves the hig...
TL;DR: Results indicate that the electrically conductive and nanofibrous networks formed by CNTs within a porous gelatin framework are the key characteristics of CNT-GelMA leading to improved cardiac cell adhesion, organization, and cell-cell coupling.
Abstract: We engineered functional cardiac patches by seeding neonatal rat cardiomyocytes onto carbon nanotube (CNT)-incorporated photo-cross-linkable gelatin methacrylate (GelMA) hydrogels. The resulting cardiac constructs showed excellent mechanical integrity and advanced electrophysiological functions. Specifically, myocardial tissues cultured on 50 μm thick CNT-GelMA showed 3 times higher spontaneous synchronous beating rates and 85% lower excitation threshold, compared to those cultured on pristine GelMA hydrogels. Our results indicate that the electrically conductive and nanofibrous networks formed by CNTs within a porous gelatin framework are the key characteristics of CNT-GelMA leading to improved cardiac cell adhesion, organization, and cell–cell coupling. Centimeter-scale patches were released from glass substrates to form 3D biohybrid actuators, which showed controllable linear cyclic contraction/extension, pumping, and swimming actuations. In addition, we demonstrate for the first time that cardiac tiss...
TL;DR: The extension of the UC excitation spectrum to shorter wavelengths, where water has lower absorption is reported, and it is confirmed that the laser-induced local overheating effect is greatly minimized.
Abstract: Upconversion (UC) process in lanthanide-doped nanomaterials has attracted great research interest for its extensive biological applications in vitro and in vivo, benefiting from the high tissue penetration depth of near-infrared excitation light and low autofluorescence background. However, the 980 nm laser, typically used to trigger the Yb3+-sensitized UC process, is strongly absorbed by water in biological structures and could cause severe overheating effect. In this article, we report the extension of the UC excitation spectrum to shorter wavelengths, where water has lower absorption. This is realized by further introducing Nd3+ as the sensitizer and by building a core/shell structure to ensure successive Nd3+→Yb3+→activator energy transfer. The efficacy of this Nd3+-sensitized UC process is demonstrated in in vivo imaging, and the results confirmed that the laser-induced local overheating effect is greatly minimized.
TL;DR: The observation of structure transition characteristics discussed in this paper provides direct explanation for the observed gradual capacity loss and poor rate performance of the layered composite and provides clues about how to improve the materials structure in order to improve electrochemical performance.
Abstract: Pristine Li-rich layered cathodes, such as Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.1Mn0.525Co0.175O2, were identified to exist in two different structures: LiMO2R3m and Li2MO3C2/m phases. Upon 300 cycles of charge/discharge, both phases gradually transform to the spinel structure. The transition from LiMO2R3m to spinel is accomplished through the migration of transition metal ions to the Li site without breaking down the lattice, leading to the formation of mosaic structured spinel grains within the parent particle. In contrast, transition from Li2MO3C2/m to spinel involves removal of Li+ and O2-, which produces large lattice strain and leads to the breakdown of the parent lattice. The newly formed spinel grains show random orientation within the same particle. Cracks and pores were also noticed within some layered nanoparticles after cycling, which is believed to be the consequence of the lattice breakdown and vacancy condensation upon removal of lithium ions. The AlF3-coating can partially relieve the spinel f...
TL;DR: The fabrication of highly porous graphene-derived carbons with hierarchical pore structures in which mesopores are integrated into macroporous scaffolds are demonstrated, which makes them potentially promising for diverse energy storage devices.
Abstract: Electric double layer capacitors (or supercapacitors) store charges through the physisorption of electrolyte ions onto porous carbon electrodes. The control over structure and morphology of carbon electrode materials is therefore an effective strategy to render them high surface area and efficient paths for ion diffusion. Here we demonstrate the fabrication of highly porous graphene-derived carbons with hierarchical pore structures in which mesopores are integrated into macroporous scaffolds. The macropores were introduced by assembling graphene-based hollow spheres, and the mesopores were derived from the chemical activation with potassium hydroxide. The unique three-dimensional pore structures in the produced graphene-derived carbons give rise to a Brunauer–Emmett–Teller surface area value of up to 3290 m2 g–1 and provide an efficient pathway for electrolyte ions to diffuse into the interior surfaces of bulk electrode particles. These carbons exhibit both high gravimetric (174 F g–1) and volumetric (∼10...
TL;DR: Inspired by the results that the electrochemical activity and electrical conductivity of ZnO nanowires were greatly improved after hydrogenation, hydrogenated single-crystal ZnNO@amorphous ZNO-doped MnO2 core-shell nanocables (HZM) on carbon cloth as SC electrodes were designed and fabricated, showing excellent performance.
Abstract: Although MnO2 is a promising material for supercapacitors (SCs) due to its excellent electrochemical performance and natural abundance, its wide application is limited by poor electrical conductivity. Inspired by our results that the electrochemical activity and electrical conductivity of ZnO nanowires were greatly improved after hydrogenation, we designed and fabricated hydrogenated single-crystal ZnO@amorphous ZnO-doped MnO2 core–shell nanocables (HZM) on carbon cloth as SC electrodes, showing excellent performance such as areal capacitance of 138.7 mF/cm2 and specific capacitance of 1260.9 F/g. Highly flexible all-solid-state SCs were subsequently assembled with these novel HZM electrodes using polyvinyl alcohol/LiCl electrolyte. The working devices achieved very high total areal capacitance of 26 mF/cm2 and retained 87.5% of the original capacitance even after 10 000 charge/discharge cycles. An integrated power pack incorporating series-wound SCs and dye-sensitized solar cells was demonstrated for sta...
TL;DR: It is shown that the two-dimensional nature of graphene oxide and its superpermeability to water combine to enable humidity sensors with unprecedented response speed (∼30 ms response and recovery times), which opens the door to various applications, such as touchless user interfaces, which is demonstrated with a 'whistling' recognition analysis.
Abstract: Sensors allow an electronic device to become a gateway between the digital and physical worlds, and sensor materials with unprecedented performance can create new applications and new avenues for user interaction. Graphene oxide can be exploited in humidity and temperature sensors with a number of convenient features such as flexibility, transparency and suitability for large-scale manufacturing. Here we show that the two-dimensional nature of graphene oxide and its superpermeability to water combine to enable humidity sensors with unprecedented response speed (∼30 ms response and recovery times). This opens the door to various applications, such as touchless user interfaces, which we demonstrate with a ‘whistling’ recognition analysis.
TL;DR: Calculations from density functional theory (DFT) are in good agreement with the proposed mechanism for band gap tuning in the GQDs through the use of functionalization.
Abstract: The band gap properties of graphene quantum dots (GQDs) arise from quantum confinement effects and differ from those in semimetallic graphene sheets. Tailoring the size of the band gap and understanding the band gap tuning mechanism are essential for the applications of GQDs in opto-electronics. In this study, we observe that the photoluminescence (PL) of the GQDs shifts due to charge transfers between functional groups and GQDs. GQDs that are functionalized with amine groups and are 1–3 layers thick and less than 5 nm in diameter were successfully fabricated using a two-step cutting process from graphene oxides (GOs). The functionalized GQDs exhibit a redshift of PL emission (ca. 30 nm) compared to the unfunctionalized GQDs. Furthermore, the PL emissions of the GQDs and the amine-functionalized GQDs were also shifted by changes in the pH due to the protonation or deprotonation of the functional groups. The PL shifts resulted from charge transfers between the functional groups and GQDs, which can tune the...
TL;DR: It is demonstrated that high-crystalline mono- and few-layer WS2 flakes and even complete layers can be synthesized on sapphire with the domain size exceeding 50 × 50 μm(2) and it is interesting to see that, only through a mild sample oxidation process, the grain boundaries are easily recognizable by scanning electron microscopy due to its altered contrasts.
Abstract: Atomically thin tungsten disulfide (WS2), a structural analogue to MoS2, has attracted great interest due to its indirect-to-direct band-gap tunability, giant spin splitting, and valley-related physics. However, the batch production of layered WS2 is underdeveloped (as compared with that of MoS2) for exploring these fundamental issues and developing its applications. Here, using a low-pressure chemical vapor deposition method, we demonstrate that high-crystalline mono- and few-layer WS2 flakes and even complete layers can be synthesized on sapphire with the domain size exceeding 50 × 50 μm2. Intriguingly, we show that, with adding minor H2 carrier gas, the shape of monolayer WS2 flakes can be tailored from jagged to straight edge triangles and still single crystalline. Meanwhile, some intersecting triangle shape flakes are concomitantly evolved from more than one nucleus to show a polycrystalline nature. It is interesting to see that, only through a mild sample oxidation process, the grain boundaries are ...
TL;DR: Fast trapping of excitons by surface trap states was observed in monolayer and few-layer structures, pointing to the importance of controlling surface properties in atomically thin crystals such as MoS₂ along with controlling their dimensions.
Abstract: Femtosecond transient absorption spectroscopy and microscopy were employed to study exciton dynamics in suspended and Si3N4 substrate-supported monolayer and few-layer MoS2 2D crystals. Exciton dynamics for the monolayer and few-layer structures were found to be remarkably different from those of thick crystals when probed at energies near that of the lowest energy direct exciton (A exciton). The intraband relaxation rate was enhanced by more than 40 fold in the monolayer in comparison to that observed in the thick crystals, which we attributed to defect assisted scattering. Faster electron–hole recombination was found in monolayer and few-layer structures due to quantum confinement effects that lead to an indirect–direct band gap crossover. Nonradiative rather than radiative relaxation pathways dominate the dynamics in the monolayer and few-layer MoS2. Fast trapping of excitons by surface trap states was observed in monolayer and few-layer structures, pointing to the importance of controlling surface pro...
TL;DR: The well-defined DINPs exhibited great potential in targeting cancer imaging and chemo-photothermal therapy and no tumor recurrence was observed after only a single dose of DINP with laser irradiation.
Abstract: A combination of chemotherapy and photothermal therapy has emerged as a promising strategy for cancer therapy. To ensure the chemotherapeutic drug and photothermal agent could be simultaneously delivered to a tumor region to exert their synergistic effect, a safe and efficient delivery system is highly desirable. Herein, we fabricated doxorubicin (DOX) and indocyanine green (ICG) loaded poly(lactic-co-glycolic acid) (PLGA)–lecithin–polyethylene glycol (PEG) nanoparticles (DINPs) using a single-step sonication method. The DINPs exhibited good monodispersity, excellent fluorescence/size stability, and consistent spectra characteristics compared with free ICG or DOX. Moreover, the DINPs showed higher temperature response, faster DOX release under laser irradiation, and longer retention time in tumor. In the meantime, the fluorescence of DOX and ICG in DINPs was also visualized for the process of subcellular location in vitro and metabolic distribution in vivo. In comparison with chemo or photothermal treatme...
TL;DR: The G-S hybrids show a high capacity, an excellent high-rate performance, and a long life over 100 cycles, demonstrating the great potential of this unique hybrid structure as cathodes for high-performance lithium-sulfur batteries.
Abstract: Graphene-sulfur (G-S) hybrid materials with sulfur nanocrystals anchored on interconnected fibrous graphene are obtained by a facile one-pot strategy using a sulfur/carbon disulfide/alcohol mixed solution. The reduction of graphene oxide and the formation/binding of sulfur nanocrystals were integrated. The G-S hybrids exhibit a highly porous network structure constructed by fibrous graphene, many electrically conducting pathways, and easily tunable sulfur content, which can be cut and pressed into pellets to be directly used as lithium-sulfur battery cathodes without using a metal current-collector, binder, and conductive additive. The porous network and sulfur nanocrystals enable rapid ion transport and short Li(+) diffusion distance, the interconnected fibrous graphene provides highly conductive electron transport pathways, and the oxygen-containing (mainly hydroxyl/epoxide) groups show strong binding with polysulfides, preventing their dissolution into the electrolyte based on first-principles calculations. As a result, the G-S hybrids show a high capacity, an excellent high-rate performance, and a long life over 100 cycles. These results demonstrate the great potential of this unique hybrid structure as cathodes for high-performance lithium-sulfur batteries.
TL;DR: Bioinspired exosome-mimetic nanovesicles that deliver chemotherapeutics to the tumor tissue after systemic administration and removal of the plasma membrane proteins by trypsinization eliminated the therapeutic effects of the nanovesicle both in vitro and in vivo are suggested.
Abstract: Exosomes, the endogenous nanocarriers that can deliver biological information between cells, were recently introduced as new kind of drug delivery system. However, mammalian cells release relatively low quantities of exosomes, and purification of exosomes is difficult. Here, we developed bioinspired exosome-mimetic nanovesicles that deliver chemotherapeutics to the tumor tissue after systemic administration. The chemotherapeutics-loaded nanovesicles were produced by the breakdown of monocytes or macrophages using a serial extrusion through filters with diminishing pore sizes (10, 5, and 1 μm). These cell-derived nanovesicles have similar characteristics with the exosomes but have 100-fold higher production yield. Furthermore, the nanovesicles have natural targeting ability of cells by maintaining the topology of plasma membrane proteins. In vitro, chemotherapeutic drug-loaded nanovesicles induced TNF-α-stimulated endothelial cell death in a dose-dependent manner. In vivo, experiments in mice showed that t...
TL;DR: This Perspective highlights different types of carbon-based nanomaterials currently used in biomedical applications, including high-strength materials and electronics.
Abstract: Functional carbon-based nanomaterials (CBNs) have become important due to their unique combinations of chemical and physical properties (i.e., thermal and electrical conductivity, high mechanical strength, and optical properties), and extensive research efforts are being made to utilize these materials for various industrial applications, such as high-strength materials and electronics. These advantageous properties of CBNs are also actively investigated in several areas of biomedical engineering. This Perspective highlights different types of carbon-based nanomaterials currently used in biomedical applications.