Copper-Halide Polymer Nanowires as Versatile Supports for Single-Atom Catalysts.

Single-atom catalysts are heterogeneous catalysts with atomistically dispersed atoms acting as a catalytically active center, and have recently attracted much attention owing to the minimal use of noble metals. However, a scalable and inexpensive support that can stably anchor isolated atoms remains a challenge due to high surface energy. Here, copper-halide polymer nanowires with sub-nanometer pores are proposed as a versatile support for single-atom catalysts. The synthesis of the nanowires is straightforward and completed in a few minutes. Well-defined sub-nanometer pores and a large free volume of the nanowires are advantageous over any other support material. The nanowires can anchor various atomistically dispersed metal atoms into the sub-nanometer pores up to ≈3 at% via a simple solution process, and this value is at least twice as big as previously reported data. The hydrogen evolution reaction activity of -18.0 A mgPt -1 at -0.2 V overpotential shows its potential for single-atom catalysts support.

One-Dimensional Cuprous Selenide Nanostructures with Switchable Plasmonic and Super-ionic Phase Attributes.

Cuprous selenide nanocrystals have hallmark attributes, especially tunable localized surface plasmon resonances (LSPRs) and super-ionic behavior. These attributes of cuprous selenide are now integrated with a one-dimensional morphology. Essentially, Cu2 Se nanowires (NWs) of micrometer-scale lengths and about 10 nm diameter are prepared. The NWs exhibit a super-ionic phase that is stable at temperatures lower than in the bulk, owing to compressive lattice strain along the radial dimension of the NWs. The NWs can be switched between oxidized and reduced forms, which have contrasting phase transition and LSPR characteristics. This work thus makes available switchable, one-dimensional waveguides and ion-conducting channels.

Designing Metallic and Insulating Nanocrystal Heterostructures to Fabricate Highly Sensitive and Solution Processed Strain Gauges for Wearable Sensors.

All-solution processed, high-performance wearable strain sensors are demonstrated using heterostructure nanocrystal (NC) solids. By incorporating insulating artificial atoms of CdSe quantum dot NCs into metallic artificial atoms of Au NC thin film matrix, metal-insulator heterostructures are designed. This hybrid structure results in a shift close to the percolation threshold, modifying the charge transport mechanism and enhancing sensitivity in accordance with the site percolation theory. The number of electrical pathways is also manipulated by creating nanocracks to further increase its sensitivity, inspired from the bond percolation theory. The combination of the two strategies achieves gauge factor up to 5045, the highest sensitivity recorded among NC-based strain gauges. These strain sensors show high reliability, durability, frequency stability, and negligible hysteresis. The fundamental charge transport behavior of these NC solids is investigated and the combined site and bond percolation theory is developed to illuminate the origin of their enhanced sensitivity. Finally, all NC-based and solution-processed strain gauge sensor arrays are fabricated, which effectively measure the motion of each finger joint, the pulse of heart rate, and the movement of vocal cords of human. This work provides a pathway for designing low-cost and high-performance electronic skin or wearable devices.

Surface Rh-Boosted Photoelectrochemical Water Oxidation of α-Fe2O3 by Reduced Overpotential in the Rate-Determining Step.

The photoelectrochemical behavior of Rh cluster-deposited hematite (α-Fe2O3) photoanodes (α-Fe2O3@Rh) was investigated. The interactions between Rh clusters and α-Fe2O3 nanorods were elucidated both experimentally and computationally. A facile UV-assisted solution casting deposition method allowed the deposition of 2 nm Rh clusters on α-Fe2O3. The deposited Rh clusters effectively enhanced the photoelectrochemical performance of the α-Fe2O3 photoanode, and electrochemical impedance spectroscopy (EIS) and Mott-Schottky analysis were applied to understand the working mechanism for the α-Fe2O3@Rh photoanodes. The results revealed a distinctive carrier transport mechanism for α-Fe2O3@Rh and increased carrier density, while the absorbance spectra remained unchanged. Furthermore, density functional theory (DFT) calculations of the oxygen evolution reaction (OER) mechanism corresponded well with the experimental results, indicating a reduced overpotential of the rate-determining step. In addition, DFT calculation models based on the X-ray diffraction (XRD) measurements and X-ray photoelectron spectroscopy (XPS) results provided precise water-splitting mechanisms for the fabricated α-Fe2O3 and α-Fe2O3@Rh nanorods. Owing to enhanced carrier generation and hole transfer, the optimum α-Fe2O3@Rh3 sample showed 78% increased photocurrent density, reaching 1.12 mA/cm-2 at 1.23 VRHE compared to that of the pristine α-Fe2O3 nanorods electrode.

Dimensional Control of Highly Anisotropic and Transparent Conductive Coordination Polymers for Solution-Processable Large-Scale 2D Sheets.

Controlling the dimensional aspect of conductive coordination polymers is currently a key scientific interest. Herein, solution-based dimension control strategies are proposed for copper chloride thiourea (CuCl-TU) coordination polymers that enable centimeter-scale, 2D nanosheet formation for use as transparent electrodes. Despite the wide bandgap of CuCl-TU polymers (4.33 eV), through polaron-mediated electron transfer, the electrical conductivity of the 2D sheet at room temperature is able to reach 4.45 S cm-1 without intentional doping. This leads to a highly anisotropic electronic conductivity of up to the order of ≈103 differences, depending on the material orientation. Furthermore, by substituting alternative thiourea candidates, it is demonstrated that it is possible to predesign CuCl-TU structures with the desired functionality, stability, and porosity through dimensional control. These findings provide a blueprint to design next-generation transparent conducting materials that can operate at room temperature, thereby expanding their applicability to different fields.

Synergistic effects of SPR and FRET on the photoluminescence of ZnO nanorod heterostructures.

Solution-grown ZnO nanorods (NRs) were successfully conjugated with CdSe/ZnS quantum dots (QDs) and Ag nanoparticles (NPs) to suppress intrinsic defect emission and to enhance band-edge emission at the same time. First, high-density and high-crystallinity ZnO NRs of diameter 80­90 nm and length 1.2­1.5 µm were grown on glass substrates using a low-temperature seed-assisted solution method. The as-synthesized ZnO NRs showed sharp photoluminescence (PL) band-edge emission centered at ∼377 nm together with broad defect emission in the range of ∼450­800 nm. The ZnO NRs were decorated with CdSe/ZnS QDs and Ag NPs, respectively, by sequential drop-coating. The PL of CdSe/ZnS QD||ZnO NR conjugates showed that ZnO band-edge emission decreased by 73.8% due to fluorescence resonance energy transfer (FRET) and charge separation between ZnO and CdSe/ZnS by type II energy band structure formation. On the other hand, Ag NP||CdSe/ZnS QD||ZnO NR conjugates showed increased band-edge emission (by 25.8%) and suppressed defect emission compared to bare ZnO NRs. A possible energy transfer mechanism to explain the improved PL properties of ZnO NRs was proposed based upon the combined effects of FRET and surface plasmon resonance (SPR).

The effect of the concentration and oxidation state of Sn on the structural and electrical properties of indium tin oxide nanowires.

High quality single-crystalline indium tin oxide (ITO) nanowires with controlled Sn contents of up to 32.5 at.% were successfully synthesized via a thermal metal co-evaporation method, based on a vapor-liquid-solid growth mode, at a substrate temperature of as low as 540 °C. The high solubility of Sn in the nanowires was explained with the existence of Sn(2+) ions along with Sn(4+) ions: the coexistence of Sn(2+) and Sn(4+) ions facilitated their high substitutional incorporation into the In(2)O(3) lattice by relaxing structural and electrical disturbances due to the differences in ionic radii and electrical charges between Sn and In(3+) ions. It was revealed that, while the lattice parameter of the ITO nanowires had a minimum value at a Sn content of 6.3 at.%, the electrical resistivity had a minimum value of about 10(-3) Ω cm at a Sn content of 14 at.%. These structural and electrical behaviors were explained by variation in the relative and total amounts of the two species, Sn(2+) and Sn(4+).

Improved electrical and reliability characteristics in metal/oxide/nitride/oxide/silicon capacitors with blocking oxide layers formed under the radical oxidation process.

We propose a Metal-Oxide-Nitride-Oxide-Silicon (MONOS) structure whose blocking oxide is formed by radical oxidation on the silicon nitride (Si3N4) layer to improve the electrical and reliability characteristics. We directly compare the electrical and reliability properties of the MONOS capacitors with two different blocking oxide (SiO2) layers, which are called a "radical oxide" grown by the radical oxidation and a "CVD oxide" deposited by chemical vapor deposition (CVD) respectively. The MONOS capacitor with a radical oxide shows a larger C-V memory window of 3.6 V at sweep voltages from 9 V to -9 V, faster program/erase speeds of 1 micros/1 ms at bias voltages of -6 V and 8 V, a lower leakage current of 7 pA and a longer data retention, compared to those of the MONOS capacitor with a CVD oxide. These improvements have been attributed to both high densification of blocking oxide film and increased nitride-related memory traps at the interface between the blocking oxide and Si3N4 layer by radical oxidation.

Enhanced IR-driven photoelectrochemical responses of CdSe/ZnO heterostructures by up-conversion UV/visible light irradiation.

We, for the first time, report the development of infrared (IR)-driven photoelectrochemical (PEC) cells using up-conversion glass-ceramics as substrates, which is different from the previous strategies of decorating photocatalysts with up-conversion (UC) rare earth-doped fluoride nanoparticles to utilize IR light. Our approach is more efficient since the use of UC glass-ceramics as substrates of photocatalysts could overcome the chemical instability of fluoride nanoparticles, the blockage of incident light, and the limited exposure of photocatalysts to liquid electrolytes. Oxyfluoride glass-ceramics bearing (Yb,Er)-doped YF3 and (Yb,Tm)-doped YF3 nanocrystals turned out to generate UC green and ultraviolet/blue emissions, respectively, under 980 nm illumination. High-density ZnO nanorods were grown on the up-conversion glass-ceramic substrates by the hydrothermal method and they were subsequently overcoated with CdSe nanocrystals to obtain CdSe/ZnO heterostructures by the chemical bath deposition method. CdSe nanoparticles were excited by both the UC UV emission from Tm and the visible emission from Er and Tm, while ZnO nanorods were excited mostly by the UC UV emission from Tm. Because of the difference in the UC emissions from Er and Tm, two distinct carrier transportations, sensitization and type-II cascade, occurred in the identical CdSe/ZnO heterostructures. Eventually, CdSe/ZnO fabricated on the glass-ceramics bearing (Yb,Tm)-doped YF3 showed increased photocurrent density compared to that fabricated on the glass-ceramics bearing (Yb,Er)-doped YF3 due to the charge separation activated by the type-II cascade structure.

The detection of platelet derived growth factor using decoupling of quencher-oligonucleotide from aptamer/quantum dot bioconjugates.

High-sensitivity, high-specificity detection of platelet derived growth factor (PDGF)-BB was realized using the change in fluorescence resonance energy transfer (FRET) occurring between quantum dot (QD) donors and black hole quencher (BHQ) acceptors. CdSe/ZnS QD/mercaptoacetic acid (MAA)/PDGF aptamer bioconjugates were successfully synthesized using ligand exchange. Black hole quencher (BHQ)-bearing oligonucleotide molecules showing partial sequence matching to PDGF aptamer were attached to PDGF aptamers and photoluminescence (PL) quenching was obtained through FRET. By adding target PDGF-BB to the bioconjugates containing BHQs, PL recovery was detected due to detachment of BHQ-bearing oligonucleotide from the PDGF aptamer as a result of the difference in affinity to the PDGF aptamer. The detection limit of the sensor was approximately 0.4 nM and the linearity was maintained up to 1.6 nM in the PL intensity versus concentration curve. Measurement of PL recovery was suggested as a strong tool for high-sensitivity detection of PDGF-BB. Epidermal growth factor (EGF), the negative control molecule, did not contribute to PL recovery due to lack of binding affinity to the PDGF aptamers, which demonstrates the selectivity of the biosensor.

Enhanced cycling performance of an Fe0/Fe3O4 nanocomposite electrode for lithium-ion batteries.

We demonstrate the formation of a highly conductive, Fe0/Fe3O4 nanocomposite electrode by the hydrogen reduction process. Fe2O3 nanobundles composed of one-dimensional nanowires were initially prepared through thermal dehydrogenation of hydrothermally synthesized FeOOH. The systematic phase and morphological evolutions from Fe2O3 to Fe2O3/Fe3O4, Fe3O4, and finally to Fe/Fe3O4 by the controlled thermochemical reduction at 300 degrees C in H2 were characterized using x-ray diffraction (XRD) and transmission electron microscopy (TEM). The Fe/Fe3O4 nanocomposite electrode shows excellent capacity retention ( approximately 540 mA h g(-1) after 100 cycles at a rate of 185 mA g(-1)), compared to that of Fe2O3 nanobundles. This enhanced electrochemical performance in Fe/Fe3O4 composites was attributed to the formation of unique, core-shell nanostructures offering an efficient electron transport path to the current collector.

Enhancement of field-emission properties in ZnO nanowire array by post-annealing in H2 ambient.

We studied the effects of post-annealing in H2 and O2 ambients on field-emission properties of vertically-aligned ZnO nanowire arrays synthesized by carbothermal reduction process. The turn-on electric field was dramatically decreased from 3.78 to 2.37 V/microm after post-annealing in H2 ambient, which was explained by both hydrogen passivation effects of deep levels and surface modification. In other words, we could observe significant decrease of deep level peak in photoluminescence measurements on hydrogen post-annealed ZnO nanowire array. And also hydrogen-related bonds are strongly increased from X-ray photoelectron spectroscopy measurements. These findings suggest that the concentration of conduction electrons increased by hydrogen post-annealing, which results in the enhanced tunneling probability of conduction electrons into the vacuum.

A Generalized Crystallographic Description of All Tellurium Nanostructures.

Despite tellurium being less abundant in the Earth's crust than gold, platinum, or rare-earth elements, the number of industrial applications of tellurium has rapidly increased in recent years. However, to date, many properties of tellurium and its associated compounds remain unknown. For example, formation mechanisms of many tellurium nanostructures synthesized so far have not yet been verified, and it is unclear why tellurium can readily transform to other compounds like silver telluride by simply mixing with solutions containing silver ions. This uncertainty appears to be due to previous misunderstandings about the tellurium structure. Here, a new approach to the tellurium structure via synthesized structures is proposed. It is found that the proposed approach applies not only to these structures but to all other tellurium nanostructures. Moreover, some unique tellurium nanostructures whose formation mechanism are, until now, unconfirmed can be explained.

Spinodally Decomposed PbSe-PbTe Nanoparticles for High-Performance Thermoelectrics: Enhanced Phonon Scattering and Unusual Transport Behavior.

Dramatic enhancements in the figure of merit have been obtained in bulk thermoelectric materials by doping, band engineering, and nanostructuring. Especially, in p-type thermoelectrics, high figure of merits near 2.0 have been reported in a few papers through the reduction in lattice thermal conductivity and the advancement in power factors. However, there exists no report on the n-type systems showing high figure of merits because of their intrinsically low Seebeck coefficients. Here, we demonstrate that a nanostructured bulk n-type thermoelectric material that was assembled by sintering spinodally decomposed lead chalcogenide nanoparticles having a composition of PbSe0.5Te0.5 reaches a high figure of merit of 1.85. The spinodally decomposed nanoparticles permit our thermoelectric material to have extremely low lattice thermal conductivity and a high power factor as a result of nanostructuring, electronic optimization, insertion of an impurity phase and phase change in local areas. We propose that this interesting concept would be one of the promising approaches that overcome limitation arising from the fact that most parameters in the figure of merit are closely correlated.

Self-catalytic solution-liquid-liquid-solid (SLLS) growth of tapered SnS nanorods.

Taper-shaped SnS nanorods were synthesized via mild chemistry, and the self-catalytic solution-liquid-liquid-solid (SLLS) process was proposed as a crystal growth mechanism. There exists a distinct difference in our SLLS growth compared to the well-known SLS growth in that we injected Sn precursors into a hot trioctylphosphine sulfide (TOPS) solution, which is a reverse process of the general SLS growth. This reverse process could prevent the oxidation of Sn precursors and thus it could facilitate the growth of SnS nanorods, since the surface of Sn clusters and droplets could be momentarily passivated by TOPS molecules. Without addition of extra catalyst nanoparticles, the nucleation and growth of SnS nanorods was induced by liquid Sn droplets. Spherical Sn tips existing at the top of the nanorods evidence the self-catalytic growth. The SLLS growth was proposed based upon the large Sn clusters existing at the bottom of the SnS nanorods in an intermediate stage (5 s) of the growth and the tapered morphology of the nanorods. The growth of SnS nanorods could progress by the upward diffusion of Sn atoms from large liquid Sn clusters along the surface of the SnS nanorods to the interfacial liquid layers (neck area) and the diffusion of S decomposed from TOPS in the solution to the neck area. SnS nanorods showed a direct energy band gap of ∼1.6 eV, determined by using the Kubelka-Munk transformation of UV-visible spectra. This self-catalytic SLLS growth produced high-quality and single crystalline SnS nanorods within only 15 s at 290 °C.

Electrochemical detection of vascular endothelial growth factors (VEGFs) using VEGF antibody fragments modified Au NPs/ITO electrode.

A new electrochemical technique for the detection of vascular endothelial growth factors (VEGFs) as a cancer-related biomarker is presented in this paper. Gold nanoparticles (Au NPs) were self-assembled onto an indium tin oxide (ITO) electrode to prepare a modified sandwich type electrochemical immunoassay platform. VEGF antibodies were cleaved into two half-fragments by 2-mercaptoethylamine-HCl (2-MEA) and the fragments were immobilized onto the Au NP substrates by their thiol groups. Through this strategy, randomly oriented attachment of antibodies was prevented which frequently occurs in a general use of whole antibody and reduces the number of available sites for the attachment of target molecules. VEGF target molecules were applied to the immunoelectrodes and they combined with the antibody fragments covering the Au NP electrode, forming antigen-antibody complexes. Then, ferrocene-tagged antibodies, which release electrons under a proper applied potential, were added to the system and they combined with the VEGF molecules pre-attached to the antibody fragments. The redox current of ferrocene measured by the differential pulse voltammetry (DPV) increased almost linearly from 1.27 x 10(-4) to 4.17 x 10(-4)A according to the increase in the concentration of the VEGF target molecules from 100 to 600 pg/ml. The measured current values represent the concentration of the VEGF since they are proportional to the number of ferrocene molecules which is in turn proportional to the concentration of VEGF target molecules. Using this modified sandwich immunoassay with the Au NP/ITO electrode, VEGFs as low as 100 pg/ml were detected with high specificity.

Kinetic analysis for formation of Cd1-xZnxSe solid-solution nanocrystals.

Kinetic analysis on the nanocrystal solid-solution formation was performed by heat treating CdSe/ZnSe core/shell nanocrystals, synthesized via a typical TOP/TOPO approach, at different temperatures for different time periods. X-ray diffraction (XRD) peak shifts in Cd1-xZnxSe cores according to the solid-solution treatments were monitored and used for the estimation of the lattice parameter change. The degree of solid-solution formation was determined considering the compositional variation in Cd1-xZnxSe cores, which was obtained from the Vegard's law. The degree of solid-solution formation (x) was applied to Jander analysis, and an Arrhenius-type plot was produced using the slopes of Jander plots. The activation energy for solid-solution formation was determined as approximately 152 kJ/mol, which evidently indicates that the diffusion of Zn2+ ions in the CdSe-ZnSe system is the governing mechanism for the Cd1-xZnxSe solid-solution formation. The Jander equation to predict the solid-solution formation kinetics for the CdSe/ZnSe core/shell systems was completed using the reaction rate constant (k).