Qingxiao Wang

Tuning upconversion through energy migration in core–shell nanoparticles

Photon upconversion is promising for applications such as biological imaging, data storage or solar cells. Here, we have investigated upconversion processes in a broad range of gadolinium-based nanoparticles of varying composition. We show that by rational design of a core-shell structure with a set of lanthanide ions incorporated into separated layers at precisely defined concentrations, efficient upconversion emission can be realized through gadolinium sublattice-mediated energy migration for a wide range of lanthanide activators without long-lived intermediary energy states. Furthermore, the use of the core-shell structure allows the elimination of deleterious cross-relaxation. This effect enables fine-tuning of upconversion emission through trapping of the migrating energy by the activators. Indeed, the findings described here suggest a general approach to constructing a new class of luminescent materials with tunable upconversion emissions by controlled manipulation of energy transfer within a nanoscopic region.

Doping Monolayer Graphene with Single Atom Substitutions

Functionalized graphene has been extensively studied with the aim of tailoring properties for gas sensors, superconductors, supercapacitors, nanoelectronics, and spintronics. A bottleneck is the capability to control the carrier type and density by doping. We demonstrate that a two-step process is an efficient way to dope graphene: create vacancies by high-energy atom/ion bombardment and fill these vacancies with desired dopants. Different elements (Pt, Co, and In) have been successfully doped in the single-atom form. The high binding energy of the metal-vacancy complex ensures its stability and is consistent with in situ observation by an aberration-corrected and monochromated transmission electron microscope.

MoS2 transistors with 1-nanometer gate lengths

A flatter route to shorter channels High-performance silicon transistors can have gate lengths as short as 5 nm before source-drain tunneling and loss of electrostatic control lead to unacceptable leakage current when the device is off. Desai et al. explored the use of MoS2 as a channel material, given that its electronic properties as thin layers should limit such leakage. A transistor with a 1-nm physical gate was constructed with a MoS2 bilayer channel and a single-walled carbon nanotube gate electrode. Excellent switching characteristics and an on-off state current ratio of ∼106 were observed. Science, this issue p. 99 Molybdenum disulfide transistors with carbon nanotube gate electrodes have channel lengths below the silicon scaling limit. Scaling of silicon (Si) transistors is predicted to fail below 5-nanometer (nm) gate lengths because of severe short channel effects. As an alternative to Si, certain layered semiconductors are attractive for their atomically uniform thickness down to a monolayer, lower dielectric constants, larger band gaps, and heavier carrier effective mass. Here, we demonstrate molybdenum disulfide (MoS2) transistors with a 1-nm physical gate length using a single-walled carbon nanotube as the gate electrode. These ultrashort devices exhibit excellent switching characteristics with near ideal subthreshold swing of ~65 millivolts per decade and an On/Off current ratio of ~106. Simulations show an effective channel length of ~3.9 nm in the Off state and ~1 nm in the On state.

Site-specific growth of Au-Pd alloy horns on Au nanorods: a platform for highly sensitive monitoring of catalytic reactions by surface enhancement Raman spectroscopy.

Surface-enhanced Raman scattering (SERS) is a highly sensitive probe for molecular detection. The aim of this study was to develop an efficient platform for investigating the kinetics of catalytic reactions with SERS. To achieve this, we synthesized a novel Au-Pd bimetallic nanostructure (HIF-AuNR@AuPd) through site-specific epitaxial growth of Au-Pd alloy horns as catalytic sites at the ends of Au nanorods. Using high-resolution electron microscopy and tomography, we successfully reconstructed the complex three-dimensional morphology of HIF-AuNR@AuPd and identified that the horns are bound with high-index {11l} (0.25 < l < 0.43) facets. With an electron beam probe, we visualized the distribution of surface plasmon over the HIF-AuNR@AuPd nanorods, finding that strong longitudinal surface plasmon resonance concentrated at the rod ends. This unique crystal morphology led to the coupling of high catalytic activity with a strong SERS effect at the rod ends, making HIF-AuNR@AuPd an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. Using the hydrogenation of 4-nitrothiophenol as a model reaction, we demonstrated that its first-order reaction kinetics could be accurately determined from this platform. Moreover, we clearly identified the superior catalytic activity of the rod ends relative to that of the rod bodies, owing to the different SERS activities at the two positions. In comparison with other reported Au-Pd bimetallic nanostructures, HIF-AuNR@AuPd offered both higher catalytic activity and greater detection sensitivity.

High‐Performance ZnO Transistors Processed Via an Aqueous Carbon‐Free Metal Oxide Precursor Route at Temperatures Between 80–180 °C

An aqueous and carbon-free metal-oxide precursor route is used in combination with a UV irradiation-assisted low-temperature conversion method to fabricate low-voltage ZnO transistors with electron mobilities exceeding 10 cm(2) /Vs at temperatures <180 °C. Because of its low temperature requirements the method allows processing of high-performance transistors onto temperature sensitive substrates such as plastic.

Two-dimensional heterostructures of V2O5 and reduced graphene oxide as electrodes for high energy density asymmetric supercapacitors

In this article, we report the synthesis of electrode materials based on two-dimensional (2D) heterostructures of V2O5 nanosheets (V2O5 NS) and reduced graphene oxide (rGO) electrodes for asymmetric supercapacitor applications. Specifically, the 2D V2O5 and rGO/V2O5 nanosheet electrodes showed a specific capacitance of 253 F g−1 and 635 F g−1, respectively at a current density of 1 A g−1. The capacitance of the heterostructures is almost 2.5 times higher than the 2D V2O5 nanosheets alone. The corresponding energy density of 39 Wh kg−1 and 79.5 Wh kg−1 were achieved for the two electrodes at a power density of 900 W kg−1 in an asymmetric supercapacitor configuration. The energy and power density using the nanosheet heterostructure are, to our knowledge, higher than any of those that were previously reported for asymmetric supercapacitors using V2O5 electrodes.

Surface modification-induced phase transformation of hexagonal close-packed gold square sheets

Conventionally, the phase transformation of inorganic nanocrystals is realized under extreme conditions (for example, high temperature or high pressure). Here we report the complete phase transformation of Au square sheets (AuSSs) from hexagonal close-packed (hcp) to face-centered cubic (fcc) structures at ambient conditions via surface ligand exchange, resulting in the formation of (100)f-oriented fcc AuSSs. Importantly, the phase transformation can also be realized through the coating of a thin metal film (for example, Ag) on hcp AuSSs. Depending on the surfactants used during the metal coating process, two transformation pathways are observed, leading to the formation of (100)f-oriented fcc Au@Ag core-shell square sheets and (110)h/(101)f-oriented hcp/fcc mixed Au@Ag nanosheets. Furthermore, monochromated electron energy loss spectroscopy reveals the strong surface plasmon resonance absorption of fcc AuSS and Au@Ag square sheet in the infrared region. Our findings may offer a new route for the crystal-phase and shape-controlled synthesis of inorganic nanocrystals.

Solution-Printed Organic Semiconductor Blends Exhibiting Transport Properties on Par with Single Crystals

Solution-printed organic semiconductors have emerged in recent years as promising contenders for roll-to-roll manufacturing of electronic and optoelectronic circuits. The stringent performance requirements for organic thin-film transistors (OTFTs) in terms of carrier mobility, switching speed, turn-on voltage and uniformity over large areas require performance currently achieved by organic single-crystal devices, but these suffer from scale-up challenges. Here we present a new method based on blade coating of a blend of conjugated small molecules and amorphous insulating polymers to produce OTFTs with consistently excellent performance characteristics (carrier mobility as high as 6.7 cm2 V−1 s−1, low threshold voltages of<1 V and low subthreshold swings <0.5 V dec−1). Our findings demonstrate that careful control over phase separation and crystallization can yield solution-printed polycrystalline organic semiconductor films with transport properties and other figures of merit on par with their single-crystal counterparts.

Ru Nanoframes with an fcc Structure and Enhanced Catalytic Properties

Noble-metal nanoframes are of great interest to many applications due to their unique open structures. Among various noble metals, Ru has never been made into nanoframes. In this study, we report for the first time an effective method based on seeded growth and chemical etching for the facile synthesis of Ru nanoframes with high purity. The essence of this approach is to induce the preferential growth of Ru on the corners and edges of Pd truncated octahedra as the seeds by kinetic control. The resultant Pd-Ru core-frame octahedra could be easily converted to Ru octahedral nanoframes of ∼2 nm in thickness by selectively removing the Pd cores through chemical etching. Most importantly, in this approach the face-centered cubic (fcc) crystal structure of Pd seeds was faithfully replicated by Ru that usually takes an hcp structure. The fcc Ru nanoframes showed higher catalytic activities toward the reduction of p-nitrophenol by NaBH4 and the dehydrogenation of ammonia borane compared with hcp Ru nanowires with roughly the same thickness.

Chiral Transformation: From Single Nanowire to Double Helix

We report a new type of water-soluble ultrathin Au-Ag alloy nanowire (NW), which exhibits unprecedented behavior in a colloidal solution. Upon growth of a thin metal (Pd, Pt, or Au) layer, the NW winds around itself to give a metallic double helix. We propose that the winding originates from the chirality within the as-synthesized Au-Ag NWs, which were induced to untwist upon metal deposition.