Yung-Jung Hsu

Au Nanostructure-Decorated TiO2 Nanowires Exhibiting Photoactivity Across Entire UV-visible Region for Photoelectrochemical Water Splitting

Here we demonstrate that the photoactivity of Au-decorated TiO2 electrodes for photoelectrochemical water oxidation can be effectively enhanced in the entire UV-visible region from 300 to 800 nm by manipulating the shape of the decorated Au nanostructures. The samples were prepared by carefully depositing Au nanoparticles (NPs), Au nanorods (NRs), and a mixture of Au NPs and NRs on the surface of TiO2 nanowire arrays. As compared with bare TiO2, Au NP-decorated TiO2 nanowire electrodes exhibited significantly enhanced photoactivity in both the UV and visible regions. For Au NR-decorated TiO2 electrodes, the photoactivity enhancement was, however, observed in the visible region only, with the largest photocurrent generation achieved at 710 nm. Significantly, TiO2 nanowires deposited with a mixture of Au NPs and NRs showed enhanced photoactivity in the entire UV-visible region. Monochromatic incident photon-to-electron conversion efficiency measurements indicated that excitation of surface plasmon resonance of Au is responsible for the enhanced photoactivity of Au nanostructure-decorated TiO2 nanowires. Photovoltage experiment showed that the enhanced photoactivity of Au NP-decorated TiO2 in the UV region was attributable to the effective surface passivation of Au NPs. Furthermore, 3D finite-difference time domain simulation was performed to investigate the electrical field amplification at the interface between Au nanostructures and TiO2 upon SPR excitation. The results suggested that the enhanced photoactivity of Au NP-decorated TiO2 in the UV region was partially due to the increased optical absorption of TiO2 associated with SPR electrical field amplification. The current study could provide a new paradigm for designing plasmonic metal/semiconductor composite systems to effectively harvest the entire UV-visible light for solar fuel production.

Dual wavelength demultiplexing by coupling and decoupling of photonic crystal waveguides

We demonstrate that the fundamental mode of the two coupled photonic crystal waveguides (PCWs) can be odd parity in a triangular photonic crystal and their dispersion curves do intersect. Thus, the PCWs are decoupled at the crossing point. By employing the decoupling at the crossing-point frequency and ultra short coupling length for another frequency, we designed a dual-wavelength demultiplexer with a coupling length of only two wavelengths and output power ratio as high as 15 dB. A loop-shape PCW is adapted to eliminate the backward energy flow.

L-cysteine-assisted growth of core-satellite ZnS-Au nanoassemblies with high photocatalytic efficiency.

Core-satellite ZnS-Au nanoassemblies, in which each of the ZnS nanospheres was surrounded by a few Au nanoparticles, have been successfully prepared with a facile L-cysteine-assisted hydrothermal approach. The density of Au nanoparticles encircling each ZnS nanosphere can be readily controlled through suitably modulating the concentration of Au added. Because of the difference in band structures between ZnS and Au, a pronounced photoinduced charge separation was observed for the as-synthesized ZnS-Au nanoassemblies. As compared to the relevant commercial products like Au-loaded P-25 TiO(2) and ZnS powders, ZnS-Au nanoassemblies exhibited superior photocatalytic performance, demonstrating their potential as an efficient photocatalyst in relevant redox reactions. Furthermore, the recycling test revealed that core-satellite nanoassemblies of ZnS-Au could be promisingly utilized in the long-term course of photocatalysis. The present study provides a new paradigm for designing the highly efficient semiconductor/metal hybrid photocatalysts that can effectively produce chemical energy from light.

Realizing Visible Photoactivity of Metal Nanoparticles: Excited-State Behavior and Electron-Transfer Properties of Silver (Ag8) Clusters.

Silver nanoclusters complexed with dihydrolipoic acid (DHLA) exhibit molecular-like excited-state properties with well-defined absorption and emission features. The 1.8 nm diameter Ag nanoparticles capped with Ag8 clusters exhibit fluorescence maximum at 660 nm with a quantum yield of 0.07%. Although the excited state is relatively short-lived (τ 130 ps), it exhibits significant photochemical reactivity. By introducing MV(2+) as a probe, we have succeeded in elucidating the interfacial electron transfer dynamics of Ag nanoclusters. The formation of MV(+•) as the electron-transfer product with a rate constant of 2.74 × 10(10) s(-1) confirms the ability of these metal clusters to participate in the photocatalytic reduction process. Basic understanding of excited-state processes in fluorescent metal clusters paves the way toward the development of biological probes, sensors, and catalysts in energy conversion devices.

Conjugated Polymer/Nanocrystal Nanocomposites for Renewable Energy Applications in Photovoltaics and Photocatalysis

Conjugated polymer/nanocrystal composites have attracted much attention for use in renewable energy applications because of their versatile and synergistic optical and electronic properties. Upon absorbing photons, charge separation occurs in the nanocrystals, generating electrons and holes for photocurrent flow or reduction/oxidation (redox) reactions under proper conditions. Incorporating these nanocrystals into conjugated polymers can complement the visible light absorption range of the polymers for photovoltaics applications or allow the polymers to sensitize or immobilize the nanocrystals for photocatalysis. Here, the current developments of conjugated polymer/nanocrystal nanocomposites for bulk heterojunction-type photovoltaics incorporating Cd- and Pb-based nanocrystals or quantum dots are reviewed. The effects of manipulating the organic ligands and the concentration of the nanocrystal precursor, critical factors that affect the shape and aggregation of the nanocrystals, are also discussed. In the conclusion, the mechanisms through which conjugated polymers can sensitize semiconductor nanocrystals (TiO2 , ZnO) to ensure efficient charge separation, as well as how they can support immobilized nanocrystals for use in photocatalysis, are addressed.

Optical Properties and Exciton Dynamics of Alloyed Core/Shell/Shell Cd1–xZnxSe/ZnSe/ZnS Quantum Dots

In this study we introduce a new method for the one-pot synthesis of core/shell/shell alloyed Cd1-xZnxSe/ZnSe/ZnS QDs and examine the effect of the shell coating on the optical properties and exciton dynamics of the alloy core. The photoluminescence (PL) quantum yield is greatly enhanced after shell growth, from 9.6% to 63%. The exciton dynamics were studied by time correlated single photon counting (TCSPC) and fit using integrated singular value decomposition global fitting (i-SVD-GF), which showed the biexponential observed lifetimes on the nanosecond time scale remain the same after shell growth. Using ultrafast transient absorption (TA) spectroscopy and SVD-GF, we have determined that surface passivation by ZnSe and ZnSe/ZnS shells reduces nonradiative recombination primarily on the picosecond time scale. These findings are helpful in directing the development of the next generation of QDs for biological labeling and other applications.

Multicolored Cd1−xZnxSe quantum dots with type-I core/shell structure: single-step synthesis and their use as light emitting diodes

We developed a single-step hot-injection process to synthesize Cd1-xZnxSe quantum dots (QDs) with tunable emission wavelengths. The multiple emission colors of the Cd1-xZnxSe QDs resulted from the variation in their compositions (x value) with the reaction time. Because of the higher reactivity of the Cd precursor, QDs whose composition was rich in CdSe were generated at the beginning of the reaction. As the reaction proceeded, the later-formed ZnSe shell was simultaneously alloyed with the core, giving rise to a progressive alloying treatment for the grown QDs. During the reaction period, the emission color of the Cd1-xZnxSe QDs shifted from red to orange, to yellow, to green and finally to blue. A light emitting diode (LED) composed of multilayers of ITO/poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)/poly(3-hexylthiophene) blended with Cd1-xZnxSe QDs/Al was fabricated to test the electroluminescence (EL) properties of the QDs. The EL results show high color purity for the emission from LED devices containing Cd1-xZnxSe QDs, revealing that the as-synthesized QDs can be easily processed and integrated into a light-emitting device without using a complicated procedure. The findings from the present work also demonstrate the advantage of using the current single-step synthetic approach to obtain a batch of Cd1-xZnxSe QDs that may emit different colors in prototype LEDs.

Au/ZnS core/shell nanocrystals as an efficient anode photocatalyst in direct methanol fuel cells.

Au/ZnS core/shell nanocrystals with controllable shell thicknesses were synthesized using a cysteine-assisted hydrothermal method. Incorporating Au/ZnS nanocrystals into the traditional Pt-catalyzed half-cell reaction led to a 43.3% increase in methanol oxidation current under light illumination, demonstrating their promising potential for metal/semiconductor hybrid nanocrystals as the anode photocatalyst in direct methanol fuel cells.

Single-crystalline mesoporous ZnO nanosheets prepared with a green antisolvent method exhibiting excellent photocatalytic efficiencies

Single-crystalline mesoporous ZnO nanosheets were prepared with a green, deep eutectic solvent based antisolvent process followed by calcination at 300 °C. The antisolvent procedure led to formation of nanosheets of a mixed composition of zinc carbonate hydroxide and ZnO, calcination of which generated the product. The product nanosheets were ultrathin with a thickness of around 10 nm and pore sizes increasing from less than 10 nm to several tens nanometers with increasing calcination time and temperature. These nanosheets exhibited excellent photocatalytic efficiencies as good as that of a commercial photocatalyst, P-25 TiO2 in terms of photocatalytic degradation of a model pollutant, methylene blue. The success is attributable to the structural advantages of the nanosheets of being ultrathin, mesoporous, and single-crystalline.

Non-catalytic and template-free growth of aligned CdS nanowires exhibiting high field emission current densities

Various CdS nanostructures, including nanoparticle film, bundles of quasi-aligned and well-aligned nanowires, were fabricated with a non-catalytic and template-free MOCVD process. The well-aligned CdS nanowires exhibit unusually high field emission current densities of 225 mA cm(-2) at the applied electric field of 20 V microm(-1).