Growth mechanism of ZnO nanostructures for ultra-high piezoelectric d(33) coefficient

A comparative morphological study of different ZnO nanostructures was carried out with different varying process parameters for energy harvesting. Molarity, temperature, growth duration and seed layer were such fundamental controlling parameters. The study brings out an outstanding piezoelectric coefficient (d(33)) of 44.33 pm/V for vertically aligned ZnO nanorod structures, considered as the highest reported d(33) value for any kind of ZnO nanostructures. XRD analysis confirms wurtzite nature of this nanorod structure with 0001] as preferential growth direction. Semiconducting characteristic of nanorods was determined with temperature induced I/V characterization.

Purifying water containing both anionic and cationic species using a (Zn, Cu)O, ZnO, and Cobalt Ferrite based multiphase adsorbent system

For the purpose of water purification, novel and low-cost adsorbents which are promising replacements for activated carbon are being actively pursued. However, a single-phase material that adsorbs both cationic and anionic species remains elusive. Hence, a low-cost, multiphase adsorbent bed that purifies water containing both anionic and cationic pollutants is a desirable alternative. We choose anionic (Congo red, Orange G) and cationic (methylene blue, malachite green) dyes as model pollutants. These dyes are chosen since they are widely found in effluents from textile, leather, fishery, and pharmaceutical industries, and their carcinogenic, mutagenic, genotoxic, and cytotoxic impact on mammalian cells is well-established. We show that ZnO, (Zn0.24Cu0.76)O and cobalt ferrite based multiphase fixed adsorbent bed efficiently adsorbs model anionic (Congo red, Orange G) and cationic (methylene blue and malachite green) pollutants, and their complex mixtures. All adsorbent phases are synthesized using room-temperature, high-yield (similar to 96-100%), green chemical processes. The nanoadsorbents are characterized by using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, and zeta potential measurements. The constituent nanophases are deliberately chosen to be beyond 50 nm, in order to avoid the nanotoxic size regime of oxides. Adsorption characteristics of each of the phases are examined. Isotherm based analysis shows that adsorption is both spontaneous and highly favorable. zeta potential measurements indicate that electrostatic interactions are the primary driving force for the observed adsorption behavior. The isotherms obtained are best described using a composite Langmuir-Freundlich model. Pseudo-first-order, rapid kinetics is observed (with adsorption rate constants as high as 0.1-0.2 min(-1) in some cases). Film diffusion is shown to be the primary mechanism of adsorption.

Contrast in luminescence characteristics (intense UV to bright visible light) of ZnO nanostructures with the variation in microstructure

We report the controlled variation of luminescence of ZnO nanostructures from intense ultraviolet to bright visible light. Deliberate addition of surfactants in the reaction medium not only leads to growth anisotropy of ZnO, but also alters the luminescence property. ZnO nanoclusters comprising of very fine particles with crystallite sizes approximate to 15-22nm were prepared in a non-aqueous medium, either from a single alcohol or from their mixtures. Introduction of the aqueous solution of the surfactant helps in altering the microstructure of ZnO nanostructure to nanorods, nanodumb-bells as well as the luminescence property. The as-prepared powder material is found to be well crystallized. Defects introduced by the surfactant in aqueous medium play an important role in substantial transition in the optical luminescence. Chromaticity coordinates were found to lie in the yellow region of color space. This gives an impression of white light emission from ZnO nanocrystals, when excited by a blue laser. Oxygen vacancy is described as the major defect responsible for visible light emission as quantified by X-ray photoelectron spectroscopy and Raman analysis.

Improved photovoltaic performance of CdSe/CdS/PbS quantum dot sensitized ZnO nanorod array solar cell

Single crystalline zinc oxide (ZnO) nanorod array has been used for the fabrication of CdSe/CdS/PbS/ZnO quantum dot sensitized solar cell (QDSSC). The ZnO nanorod array photoanodes are sensitized with consecutive layer of PbS, CdS and CdSe quantum dots by employing simple successive ion layer adsorption and reaction (SILAR) and chemical bath deposition (CBD) techniques. The performances of the QDSSCs are examined in detail using polysulfide electrolyte with copper sulfide (CuS) counter electrode. The combination of two successive layers of PbS with CdSe/CdS/ZnO shows an improved short circuit current density (12.223 mA cm(-2)) with a maximum power to conversion efficiency of 2.352% under 1 sun illumination. This enhancement is mainly attributed due to the better light harvesting ability of the PbS quantum dots and make large accumulation of photo-injected electrons in the conduction band of ZnO, and CdSe/CdS layers lower the recombination of photo-injected electrons with the electrolyte, these are well evidenced with the photovoltaic studies and electrochemical impedance spectroscopy. (C) 2013 Elsevier B.V. All rights reserved.

Effect of post-deposition annealing on transverse piezoelectric coefficient and vibration sensing performance of ZnO thin films

The present experimental study investigates the influence of post-deposition annealing on the transverse piezoelectric coefficient (d(31)) value of ZnO thin films deposited on a flexible metal alloy substrate, and its relationship with the vibration sensing performance. Highly c-axis oriented and crystalline ZnO thin films were deposited on flexible Phynox alloy substrate via radio frequency (RF) reactive magnetron sputtering. ZnO thin film samples were annealed at different temperatures ranging from 100 degrees C to 500 degrees C, resulting in the temperature of 300 degrees C determined as the optimum annealing temperature. The crystallinity, morphology, microstructure, and rms surface roughness of annealed ZnO thin films were systematically investigated by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM), respectively. The piezoelectric d(31) coefficient value was measured by 4-point bending method. ZnO thin film annealed at 300 degrees C was highly c-axis oriented, crystalline, possesses fine surface morphology with uniformity in the grain size. This film showed higher d(31) coefficient value of 7.2 pm V-1. A suitable in-house designed and developed experimental set-up, for evaluating the vibration sensing performance of annealed ZnO thin films is discussed. As expected the ZnO thin film annealed at 300 degrees C showed relatively better result for vibration sensing studies. It generates comparatively higher peak output voltage of 147 mV, due to improved structural and morphological properties, and higher piezoelectric d(31) coefficient value. (C) 2014 Elsevier B. V. All rights reserved.

Vertically aligned ZnO nanorods on flexible substrates for multifunctional device applications: Easy and cost-effective route

Zinc oxide nanorods (ZnO NRs) have been synthesized on flexible substrates by adopting a new and novel three-step process. The as-grown ZnO NRs are vertically aligned and have excellent chemical stoichiometry between its constituents. The transmission electron microscopic studies show that these NR structures are single crystalline and grown along the < 001 > direction. The optical studies show that these nanostructures have a direct optical band gap of about 3.34 eV. Therefore, the proposed methodology for the synthesis of vertically aligned NRs on flexible sheets launches a new route in the development of low-cost flexible devices. (C) 2014 Elsevier B.V. All rights reserved.

Multivalent Cu-Doped ZnO Nanoparticles with Full Solar Spectrum Absorbance and Enhanced Photoactivity

Full solar spectrum absorbers are widely pursued for applications related to photocatalysis and photovoltaics. Here we report multivalent Cu-doped ZnO nanoparticles which exhibit full solar spectrum absorbance and high photoactivity. Metathesis-based, green-chemical approaches with synthesis yield of similar to 100% are used. Cu incorporation in ZnO results in an increase of average solar spectrum absorbance from a mere 0.4% to 34%. On the other hand, (Zn, Cu)0 composites result in materials with up to 64% average solar spectrum absorbance. Doped systems operate well under both visible and UV illumination. The nanomaterials prepared are characterized by using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, and X-ray photoelectron spectroscopy (XPS). Photocatalysts explored have particle sizes >= 50 nm. This is deliberately done in order to avoid the nanotoxic size regime of ZnO. Despite the large particle size and low specific surface area (<20 m(2).g(-1)), the best catalyst reported here compare favorably with recent reports on ZnO based systems. Using X-photoelectron spectroscopy and synthesis property correlations, we infer that the presence of multivalent Cu (most likely in the form of Cu1+delta) on ZnO surface is responsible for the observed photoactivity enhancement.

Quantum-Confined ZnO Nanoshell Photoanodes for Mesoscopic Solar Cells

We present a photoanode for dye-sensitized solar cell (DSC) based on ZnO nanoshell deposited by atomic layer deposition at 150 degrees C on a mesoporous insulating template. An ultrathin layer of ZnO between. 3 and 6 nm, which exhibits quantum confinement effect, is found to be sufficient to transport the photogenerated electrons to the external contacts and exhibits near-unity collection efficiency. A 6 nm ZnO nanoshell on a 2.5 mu m mesoporous nanoparticle Al2O3 template yields photovoltaic power conversion efficiency (PCE) of 4.2% in liquid DSC. Perovskite absorber (CH3NH3PbI3) based solid state solar cells made with similar ZnO nanostructures lead to a high PCE of 7%.

Morphology controlled synthesis of wurtzite ZnS nanostructures through simple hydrothermal method and observation of white light emission from ZnO obtained by annealing the synthesized ZnS nanostructures

A controllable synthesis of phase pure wurtzite (WZ) ZnS nanostructures has been reported in this work at a low temperature of similar to 220 degrees C using ethylenediamine as the soft template and by varying the molar concentration of zinc to sulphur precursors as well as by using different precursors. A significant reduction in the formation temperature required for the synthesis of phase pure WZ ZnS has been observed. A strong correlation has been observed between the morphology of the synthesized ZnS nanostructures and the precursors used during synthesis. It has been found from Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) image analyses that the morphology of the ZnS nanocrystals changes from a block-like to a belt-like structure having an average length of similar to 450 nm when the molar ratio of zinc to sulphur source is increased from 1 : 1 to 1 : 3. An oriented attachment (OA) growth mechanism has been used to explain the observed shape evolution of the synthesized nanostructures. The synthesized nanostructures have been characterized by the X-ray diffraction technique as well as by UV-Vis absorption and photoluminescence (PL) emission spectroscopy. The as-synthesized nanobelts exhibit defect related visible PL emission. On isochronal annealing of the nanobelts in air in the temperature range of 100-600 degrees C, it has been found that white light emission with a Commission Internationale de I'Eclairage 1931 (CIE) chromaticity coordinate of (0.30, 0.34), close to that of white light (0.33, 0.33), can be obtained from the ZnO nanostructures obtained at an annealing temperature of 600 degrees C. UV light driven degradation of methylene blue (MB) dye aqueous solution has also been demonstrated using as-synthesized nanobelts and similar to 98% dye degradation has been observed within only 40 min of light irradiation. The synthesized nanobelts with visible light emission and having dye degradation activity can be used effectively in future optoelectronic devices and in water purification for cleaning of dyes.

Evaluation. of Transverse Piezoelectric Coefficient of ZnO Thin Films Deposited on Different Flexible Substrates: A Comparative Study on the Vibration Sensing Performance

We report on the systematic comparative study of highly c-axis oriented and crystalline piezoelectric ZnO thin films deposited on four different flexible substrates for vibration sensing application. The flexible substrates employed for present experimental study were namely a metal alloy (Phynox), metal (aluminum), polyimide (Kapton), and polyester (Mylar). ZnO thin films were deposited by an RF reactive magnetron sputtering technique. ZnO thin films of similar thicknesses of 700 +/- 30 nm were deposited on four different flexible substrates to have proper comparative studies. The crystallinity, surface morphology, chemical composition, and roughness of ZnO thin films were evaluated by respective material characterization techniques. The transverse piezoelectric coefficient (d(31)) value for assessing the piezoelectric property of ZnO thin films on different flexible substrates was measured by a four-point bending method. ZnO thin films deposited on Phynox alloy substrate showed relatively better material characterization results and a higher piezoelectric d(31) coefficient value as compared to ZnO films on metal and polymer substrates. In order to experimentally verify the above observations, vibration sensing studies were performed. As expected, the ZnO thin film deposited on Phynox alloy substrate showed better vibration sensing performance. It has generated the highest peak to peak output voltage amplitude of 256 mV as compared to that of aluminum (224 mV), Kapton (144 mV), and Mylar (46 mV). Therefore, metal alloy flexible substrate proves to be a more suitable, advantageous, and versatile choice for integrating ZnO thin films as compared to metal and polymer flexible substrates for vibration sensing applications. The present experimental study is extremely important and helpful for the selection of a suitable flexible substrate for various applications in the field of sensor and actuator technology.

Detailed understanding of the excitation-intensity dependent photoluminescence of ZnO materials: Role of defects

The photoluminescence (PL) of ZnO is shown to be dependent on the excitation intensity (EI) of the laser, and the substantial shift observed in the band to band transition is attributed to the heating effect. In order to understand this phenomenon in detail, we investigate the EI dependent PL of various ZnO samples systematically from liquid nitrogen (LN) to room temperature by varying the laser power. Some of the samples exhibit substantial red shift in the band to band transition with increasing EI even in LN environment, negligible effect is observed for others. Hence, our results strongly suggest that the EI dependent PL is not a characteristic of all ZnO samples. This indicates that laser-induced heating effect is not the dominant factor that governs the shifts in the PL spectra. Rather, the defect level excitation accounts for such observation. (C) 2014 AIP Publishing LLC.

Multistage effect in enhancing the field emission behaviour of ZnO branched nanostructures

We report the synthesis of branched ZnO nanostructures by vapour phase transport and their multistage effect in enhancing the field emission behaviour. First, the ZnO nanowires (first generation) are grown and second generation nanowires are grown on first one and so on to obtain the branched structures. The number of branches increases and the diameter of the branches decreases till the third generation nanowires. Fourth generation onwards, dense branched structures are obtained eventually yielding nanoforest-like morphology. The field emission behaviour is found to improve till the third generation and is assigned to smaller diameter of the branches. (C) 2014 AIP Publishing LLC.

Influence of film thickness on the properties of sprayed ZnO thin films for gas sensor applications

Transparent conducting ZnO films were prepared at substrate temperature 400 degrees C with different film thicknesses by nebulizer spray pyrolysis method on glass substrates. XRD studies reveal that the films are polycrystalline in nature having hexagonal crystal structure with preferred grain orientations along (0 0 2) and (1 0 1) directions. The crystallite size increases along (0 0 2) plane with the thickness increase and attains a maximum 109 nm for 913 nm film thickness. Analysis of structural parameters indicates that the films having thickness 913 nm are found to have minimum dislocation density and strain values. The HRSEM measurements show that the surface morphology of the films also changes with film thickness. EDAX estimates the average atomic percentage ratio of Zn and O in the ZnO films. Optical studies reveal the band gap energy decrease from 3.27 to 3.14 eV with increase of film thickness. Room temperature PL spectra show the near-band-edge emission and deep-level emission due to the presence of defects in the ZnO thin films. Impedance spectroscopy analysis indicates that grain boundary resistance decreases with the increasing ammonia concentration up to 500 ppm and the maximum sensitivity is found to be 1.7 for 500 ppm of ammonia. (C) 2014 Elsevier Ltd. All rights reserved.

Synthesis of self-light-scattering wrinkle structured ZnO photoanode by sol-gel method for dye-sensitized solar cells

A special morphological zinc oxide (ZnO) photoanode for dye-sensitized solar cell was fabricated by simple sol-gel drop casting technique. This film shows a wrinkled structure resembling the roots of banyan tree, which acts as an effective self scattering layer for harvesting more visible light and offers an easy transport path for photo-injected electrons. These ZnO electrode of low thickness (similar to 5 mu m) gained an enhanced short-circuit current density of 6.15 mA/cm(2), open-circuit voltage of 0.67 V, fill factor of 0.47 and overall conversion efficiency of 1.97 % under 1 sun illumination. This shows a high conversion efficiency and a superior performance than that of ZnO nanoparticle-based photoanode (eta similar to 1.13 %) of high thickness (similar to 8 mu m).