K. T. Leung

Controlled Growth of Two-Dimensional and One-Dimensional ZnO Nanostructures on Indium Tin Oxide Coated Glass by Direct Electrodeposition

A simple electrochemical deposition technique is used to deposit ZnO nanostructures with diverse morphology directly on ITO-coated glass substrates at 70 degrees C. The concentration of the Zn(NO 3) 2.6H 2O electrolyte is important to controlling the dimensionality of the nanostructures, with formation of one-dimensional (1D) nanospikes and nanopillars (with 50-500 nm diameter) below 0.01 M and of two-dimensional (2D) nanowalls and nanodisks (with 50-100 nm wall/disk thickness) above 0.05 M. Glancing-incidence X-ray diffraction study shows their wurtzite structure and confirms the change in the preferred crystal plane orientation with the dimensionality of ZnO nanostructures. UV-vis spectroscopy reveals a higher transmittance from 2D nanostructures than from 1D nanostructures and their optical direct band gaps estimated to be 3.12-3.27 eV. Depth-profiling X-ray photoemission studies show the presence of Zn(OH) 2 outer layers on the ZnO nanostructures, with a higher Zn(OH) 2 moiety for 2D nanostructures relative to 1D nanostructures. Furthermore, a substantial quantity of Cl (provided by the KCl supporting electrolyte) is detected throughout the 2D nanostructures only. The photoemission data therefore affirm our proposed growth mechanism that involves capping of the preferred [0001] growth direction by Cl (-) ions under fast hydroxylation kinetics condition as observed at a higher Zn(NO 3) 2.6H 2O electrolyte concentration.

Nanoscale Shape and Size Control of Cubic, Cuboctahedral, and Octahedral Cu−Cu2O Core−Shell Nanoparticles on Si(100) by One-Step, Templateless, Capping-Agent-Free Electrodeposition

Cu-Cu2O core-shell nanoparticles (NPs) of different shapes over an extended nanosize regime of 5-400 nm have been deposited on a H-terminated Si(100) substrate by using a simple, one-step, templateless, and capping-agent-free electrochemical method. By precisely controlling the electrolyte concentration [CuSO4 x 5H2O] below their respective critical values, we can obtain cubic, cuboctahedral, and octahedral NPs of different average size and number density by varying the deposition time under a few seconds (<6 s). Combined glancing-incidence X-ray diffraction and depth-profiling X-ray photoelectron spectroscopy studies show that these NPs have a crystalline core-shell structure, with a face-centered cubic metallic Cu core and a simple cubic Cu2O shell with a CuO outerlayer. The shape control of Cu-Cu2O core-shell NPs can be understood in terms of a diffusion-limited progressive growth model under different kinetic conditions as dictated by different [CuSO4 x 5H2O] concentration regimes.

High-Performance, Flexible Enzymatic Glucose Biosensor Based on ZnO Nanowires Supported on a Gold-Coated Polyester Substrate

The present work demonstrates the fabrication and performance of an enzymatic glucose biosensor based on ZnO nanowires (NWs) deposited on a Au-coated polyester (PET) substrate. Electrodeposition of ZnO NWs on the conducting PET substrate was carried out at 70 degrees C in an aqueous electrolyte consisting of zinc nitrate mixed with potassium chloride. Glucose oxidase (GOx) was subsequently immobilized on the as-synthesized ZnO NWs, and the electrocatalytic properties of GOx-immobilized ZnO NWs were evaluated by amperometry. The resulting GOx/ZnO-NWs/Au/PET bioelectrode exhibits excellent electrocatalytic performance with a high sensitivity of 19.5 muA mM(-1) cm(-2), a low Michaelis-Menten constant of 1.57 mM, and a fast response time of <5 s for the amperometric detection of glucose. The present study illustrates the feasibility of realizing light-weight, flexible, high-performance sensing devices using ZnO NWs.

High-efficiency hybrid solar cells by nanostructural modification in PEDOT:PSS with co-solvent addition†

Conducting polymer poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) is gaining technological importance for the fabrication of organic and organic–inorganic heterostructure devices. The conductivity of PEDOT:PSS can be improved by the addition of co-solvents. Here, we show that the simple addition of a suitable wt% of a co-solvent, either ethylene glycol (EG) or dimethyl sulfoxide (DMSO), in PEDOT:PSS can significantly enhance the performance of hybrid solar cells. We provide a morphological model to explain the influence of the co-solvents in PEDOT:PSS, in which the co-solvent modifies the internal crystalline ordering of individual PEDOT nanocrystals that increases the crystal size and forms closely packed nanocrystals, and it also facilitates rearrangement of PSS that reduces its surface chain networks to enhance the polymer conductivity and hybrid solar cell properties. A hybrid solar cell made of EG 7 wt% modified PEDOT:PSS on planar Si exhibits an exceptionally high power conversion efficiency exceeding 12% for the first time.

Green Synthesis of Anatase TiO2 Nanocrystals with Diverse Shapes and their Exposed Facets-Dependent Photoredox Activity

The exposed facets of a crystal are known to be one of the key factors to its physical, chemical and electronic properties. Herein, we demonstrate the role of amines on the controlled synthesis of TiO2 nanocrystals (NCs) with diverse shapes and different exposed facets. The chemical, physical and electronic properties of the as-synthesized TiO2 NCs were evaluated and their photoredox activity was tested. It was found that the intrinsic photoredox activity of TiO2 NCs can be enhanced by controlling the chemical environment of the surface, i.e.; through morphology evolution. In particular, the rod shape TiO2 NCs with ∼25% of {101} and ∼75% of {100}/{010} exposed facets show 3.7 and 3.1 times higher photocatalytic activity than that of commercial Degussa P25 TiO2 toward the degradation of methyl orange and methylene blue, respectively. The higher activity of the rod shape TiO2 NCs is ascribed to the facetsphilic nature of the photogenerated carriers within the NCs. The photocatalytic activity of TiO2 NCs are found to be in the order of {101}+{100}/{010} (nanorods) > {101}+{001}+{100}/{010} (nanocuboids and nanocapsules) > {101} (nanoellipsoids) > {001} (nanosheets) providing the direct evidence of exposed facets-depended photocatalytic activity.

Fabrication of ZnO nanospikes and nanopillars on ITO glass by templateless seed-layer-free electrodeposition and their field-emission properties.

A simple and direct electrodeposition technique is employed to fabricate ZnO nanospikes and nanopillars on indium-tin oxide glass substrates at 70 degrees C without using any template, catalyst, or seed layer. Both ZnO nanospikes and nanopillars exhibit highly crystalline ZnO wurtzite structure with a preferred (0001) plane orientation in their high-resolution transmission electron microscopic images and X-ray diffraction patterns. The corresponding Raman spectra provide evidence for the presence of defects and oxygen vacancies in these nanostructures, which could produce the photoluminescence observed in the visible region. X-ray photoelectron spectroscopy further indicates the presence of a Zn(OH)2-rich surface region in these ZnO nanostructures and that a higher Zn(OH)2 surface moiety is found for nanospikes than nanopillars. In contrast to the nanopillars with flat tops, the nanospikes with tapered tips of 20-50 nm diameter provide a favorable geometry to facilitate excellent field-emission performance, with a low turn-on electric field of 3.2 V/microm for 1.0 microA/cm(2) and a threshold field of 6.6 V/microm for 1.0 mA/cm(2). The superior field-emission property makes the nanospikes among the best ZnO field emitters fabricated on a glass substrate at low temperature.

Defect-rich decorated TiO2 nanowires for super- efficient photoelectrochemical water splitting driven by visible light†

Oxygen vacancy defects are highly desirable for photoelectrochemical water splitting reactions of TiO2 nanomaterials because they act as electron donors and thereby enhance the electrical conductivity and charge transport property of TiO2. For TiO2 nanowires reported to date, oxygen vacancies are mainly generated by post-treatment of the as-synthesized nanowires. This comes with a disadvantage that oxygen vacancies are found to form just within a few tens of nanometers at the outer surface of these nanowires, and the photocurrent density is significantly reduced by two to three orders of magnitude when ultraviolet light is filtered out from the AM 1.5G light. Here, we demonstrate, for the first time, the controlled growth of 1D TiO2 nanostructures with different morphologies and with incorporation of oxygen vacancy defects on a Si substrate by a single-step, catalyst-assisted pulsed laser deposition (PLD) method. Photoelectrochemical water splitting measurements under simulated sunlight show that the decorated nanowires exhibit one of the highest photoactivity values in the visible region (>430 nm) reported to date, which represents 87% of the overall photocurrent. The higher activity in the visible region can be attributed to more conductive TiO2 nanostructures (i.e., with a larger amount of oxygen vacancy defects), and the enhanced charge transfer from the nanocrystallites to the core of the decorated nanowires.

Bimetallic nanoparticles for arsenic detection.

Effective and sensitive monitoring of heavy metal ions, particularly arsenic, in drinking water is very important to risk management of public health. Arsenic is one of the most serious natural pollutants in soil and water in more than 70 countries in the world. The need for very sensitive sensors to detect ultralow amounts of arsenic has attracted great research interest. Here, bimetallic FePt, FeAu, FePd, and AuPt nanoparticles (NPs) are electrochemically deposited on the Si(100) substrate, and their electrochemical properties are studied for As(III) detection. We show that trace amounts of As(III) in neutral pH could be determined by using anodic stripping voltammetry. The synergistic effect of alloying with Fe leads to better performance for Fe-noble metal NPs (Au, Pt, and Pd) than pristine noble metal NPs (without Fe alloying). Limit of detection and linear range are obtained for FePt, FeAu, and FePd NPs. The best performance is found for FePt NPs with a limit of detection of 0.8 ppb and a sensitivity of 0.42 μA ppb(-1). The selectivity of the sensor has also been tested in the presence of a large amount of Cu(II), as the most detrimental interferer ion for As detection. The bimetallic NPs therefore promise to be an effective, high-performance electrochemical sensor for the detection of ultratrace quantities of arsenic.

Size-Selected TiO2 Nanocluster Catalysts for Efficient Photoelectrochemical Water Splitting

Nanoclusters (NCs) are of great interest because they provide the link between the distinct behavior of atoms and nanoparticles and that of bulk materials. Here, we report precisely controlled deposition of size-selected TiO2 NCs produced by gas-phase aggregation in a special magnetron sputtering system. Carefully optimized aggregation length and Ar gas flow are used to control the size distribution, while a quadrupole mass filter provides precise in situ size selection (from 2 to 15 nm). Transmission electron microscopy studies reveal that NCs larger than a critical size (∼8 nm) have a crystalline core with an amorphous shell, while those smaller than the critical size are all amorphous. The TiO2 NCs so produced exhibit remarkable photoelectrochemical water splitting performance in spite of a small amount of material loading. NCs of three different sizes (4, 6, and 8 nm) deposited on H-terminated Si(100) substrates are tested for the photoelectrochemical catalytic performance, and significant enhancement in photocurrent density (0.8 mA/cm(2)) with decreasing NC size is observed with a low saturation voltage of -0.22 V vs Ag/AgCl (0.78 V vs RHE). The enhanced photoconductivity could be attributed to the increase in the specific surface area and increase in the number of active (defect) sites in the amorphous NCs. The unique advantages of the present technique will be further exploited to develop applications based on tunable, size-selected NCs.

Growth of self-assembled copper nanostructure on conducting polymer by electrodeposition

In the present work, self-assembled nanostructures of copper are grown by electrodeposition on a thin conducting polymer (polypyrrole) film electropolymerized on a gold electrode. The shapes, sizes and the densities of the nanostructures are found to depend on the thickness of the polypyrrole thin film, which provides an easy means to control the morphology of these nanostructures. In particular, for the same applied potential on the gold electrode, smaller nanocrystals with a higher density are observed on thinner polymer films while bigger nanocrystals at a lower density are found on thicker films.