Self-Assembled, Aligned ZnO Nanorod Buffer Layers for High-Current-Density, Inverted Organic Photovoltaics

Two different soft-chemical, self-assembly-based solution approaches are employed to grow zinc oxide (ZnO) nanorods with controlled texture. The methods used involve seeding and growth on a substrate. Nanorods with various aspect ratios (1-5) and diameters (15-65 nm) are grown. Obtaining highly oriented rods is determined by the way the substrate is mounted within the chemical bath. Furthermore, a preheat and centrifugation step is essential for the optimization of the growth solution. In the best samples, we obtain ZnO nanorods that are almost entirely oriented in the (002) direction; this is desirable since electron mobility of ZnO is highest along this crystallographic axis. When used as the buffer layer of inverted organic photovoltaics (I-OPVs), these one-dimensional (1D) nanostructures offer: (a) direct paths for charge transport and (b) high interfacial area for electron collection. The morphological, structural, and optical properties of ZnO nanorods are studied using scanning electron microscopy, X-ray diffraction, and ultraviolet-visible light (UV-vis) absorption spectroscopy. Furthermore, the surface chemical features of ZnO films are studied using X-ray photoelectron spectroscopy and contact angle measurements. Using as-grown ZnO, inverted OPVs are fabricated and characterized. For improving device performance, the ZnO nanorods are subjected to UV-ozone irradiation. UV-ozone treated ZnO nanorods show: (i) improvement in optical transmission, (ii) increased wetting of active organic components, and (iii) increased concentration of Zn-O surface bonds. These observations correlate well with improved device performance. The devices fabricated using these optimized buffer layers have an efficiency of similar to 3.2% and a fill factor of 0.50; this is comparable to the best I-OPVs reported that use a P3HT-PCBM active layer.

Synthesis and photocatalytic performance of quasi-fibrous ZnO

The combustion of oxidizer zinc nitrate and fuel oxalic acid results in quasi-fibrous zinc oxide. The processing parameters including oxidizer to fuel ratio, time and temperature were optimized for the resultant crystal structure and morphology. Pure hexagonal phase formation does not depend on the fuel ratio, but a stoichiometric ratio of oxidizer to fuel at 450 degrees C and 30 min results in highly crystalline ZnO with 3 mu m length and 0.5 mu m width. This quasi-fiber originates from partial fusion of near spherical, similar to 60 nm particles during the rapid rate of reaction in the combustion process. Transmission electron microscopic analysis confirms the anisotropic primary particle orientation and pore distribution within the developed quasi-fibrous particles. The degradation of methyl orange was assessed by degrading the dye in the presence of the synthesized ZnO (2.95 eV) under both UV and visible light. Quasi-fibrous zinc oxide exhibits effective photocatalytic efficiency under visible light irradiation.

Enhancing the photocatalytic efficiency of sprayed ZnO thin films through double doping (Sn plus F) and annealing under different ambiences

Doubly (Sn + F) doped zinc oxide (ZnO:Sn:F) thin films were deposited onto glass substrates using a simplified spray pyrolysis technique. The deposited films were annealed at 400 degrees C under two different ambiences (air and vacuum) for 2 h. The photocatalytic activity of these films was assessed through photocatalytic decolorization kinetics of Methylene Blue (MB) dye and the decolorization efficiency of the annealed films was compared with that of their as-deposited counterpart. The photocatalytic studies reveal that the ZnO:Sn:F films annealed under vacuum environment exhibits better photocatalytic efficiency when compared with both air annealed and as-deposited films. The SEM and TEM images depict that the surface of each of the films has an overlayer comprising of nanobars formed on a bottom layer, having spherical grains. The studies show that the diameter of the nanobars plays crucial role in enhancing the photocatalytic activity of the ZnO:Sn:F films. The structural, optical and electrical studies substantiate the discussions on the photocatalytic ability of the deposited films. (C) 2014 Elsevier B.V. All rights reserved.

ZnO/ITO core/shell nanostructure electrodes for future prototype solar cell devices

The impact of indium tin oxide (ITO) layers over vertically aligned zinc oxide nanorods (ZnO NRs) has been investigated to consider ITO nanolayers as transparent conducting oxide electrodes (TCOE) for hierarchical heteronanostructure solar cell devices that have ZnO nanostructures as branches. ZnO/ITO core/shell nanostructures were prepared in two- steps using vapor-liquid-solid and evaporation processes, and further the structures were annealed at various temperatures. Transmission electron microscopic studies show that the as-grown ZnO/ITO structures consist of an amorphous ITO shell on single crystalline ZnO cores, whereas the structures annealed above 300 degrees C consist of a single crystalline ITO shell. ITO layer deposited ZnO NRs exhibit a small red-shift in ZnO near-band-edge emission as well as optical band gap. The electrical measurements carried out on single ZnO/ITO core/shell NR under dark and UV light showed excellent thermionic transport properties. From these investigations it is emphasized that ITO nanolayers could be used as TCO electrodes for prototype ZnO based hierarchical solar cell devices.

Highly efficient WO3-ZnO mixed oxides for photocatalysis

Monoclinic nanocuboid WO3 enhanced the photocatalyst efficiency of quasi nanobelt zinc oxide for dye degradation in the presence of visible light radiation. Combustion synthesized ZnO resulted in a belt-like morphology through in situ cluster formation of near spherical particles but homogenously disperses and strongly adheres to nanocuboid WO3 during physical mixing. Cationic methylene blue (MB) and anionic orange G (OG) undergo degradation through a charge transfer mechanism in the presence of WO3-ZnO (1 : 9 weight percentage ratio) mixture. The photocatalytic reaction was enhanced due to the reduction in the recombination of photogenerated electron-holes. The high degree of 90% degradation of both dyes is due to the activity of the mixed oxides, which is much higher than that obtained either with WO3 or ZnO individually.

Highly efficient WO3-ZnO mixed oxides for photocatalysis

Monoclinic nanocuboid WO3 enhanced the photocatalyst efficiency of quasi nanobelt zinc oxide for dye degradation in the presence of visible light radiation. Combustion synthesized ZnO resulted in a belt-like morphology through in situ cluster formation of near spherical particles but homogenously disperses and strongly adheres to nanocuboid WO3 during physical mixing. Cationic methylene blue (MB) and anionic orange G (OG) undergo degradation through a charge transfer mechanism in the presence of WO3-ZnO (1 : 9 weight percentage ratio) mixture. The photocatalytic reaction was enhanced due to the reduction in the recombination of photogenerated electron-holes. The high degree of 90% degradation of both dyes is due to the activity of the mixed oxides, which is much higher than that obtained either with WO3 or ZnO individually.

Morphology controlled synthesis of Al doped ZnO nanosheets on Al alloy substrate by low-temperature solution growth method

We report the morphology-controlled synthesis of aluminium (Al) doped zinc oxide (ZnO) nanosheets on Al alloy (AA-6061) substrate by a low-temperature solution growth method without using any external seed layer and doping process. Doped ZnO nanosheets were obtained at low temperatures of 60-90 degrees C for the growth time of 4 hours. In addition to the synthesis, the effect of growth temperature on the morphological changes of ZnO nanosheets is also reported. As-synthesized nanosheets are characterized by FE-SEM, XRD TEM and XPS for their morphology, crystallinity, microstructure and compositional analysis respectively. The doping of Al in ZnO nanosheets is confirmed with EDXS and XPS. Furthermore, the effect of growth temperature on the morphological changes was studied in the range of 50 to 95 degrees C. It was found that the thickness and height of the nanosheets varied with respect to the growth temperature. The study has given an important insight into the structural morphology with respect to the growth temperature, which in turn enabled us to determine the growth temperature window for the ZnO nanosheets. These Al doped ZnO nanosheets have potential application possibilities in gas sensors, solar cells and energy harvesting devices like nanogenerators.

Synthesis, luminescence properties and EPR investigation of hydrothermally derived uniform ZnO hexagonal rods

One-dimensional (1D) zinc oxide (ZnO) hexagonal rods have been successfully synthesized by surfactant free hydrothermal process at different temperatures. It can be found that the reaction temperature play a crucial role in the formation of ZnO uniform hexagonal rods. The possible formation processes of 1-D ZnO hexagonal rods were investigated. The zinc hydroxide acts as the morphology-formative intermediate for the formation of ZnO nanorods. Upon excitation at 325 nm, the sample prepared at 180 degrees C show several emission bands at 400 nm (similar to 3.10 eV), 420 nm (similar to 2.95 eV), 482 nm (similar to 2.57 eV) and 524 nm (similar to 2.36 eV) corresponding to different kind of defects. TL studies were carried out by pre-irradiating samples with gamma-rays ranging from 1 to 7 kGy at room temperature. A well resolved glow peak at similar to 354 degrees C was recorded which can be ascribed to deep traps. Furthermore, the defects associated with surface states in ZnO nano-structures are characterized by electron paramagnetic resonance. (C) 2014 Elsevier B.V. All rights reserved.

Few-layer graphene/ZnO nanowires based high performance UV photodetector

A graphene and zinc oxide nanowires (G/ZnO NWs) based ultraviolet (UV) photodetector presents excellent responsivity and photocurrent gain with detectivity. Graphene due to higher charge carrier transport mobility induces faster response to UV illumination at the interface between ZnO and graphene with improved response and decay times as compared to a ZnO NWs device alone. A linear increase is revealed for both the responsivity and photocurrent gain of the G/ZnO NWs device with the applied bias. These results suggest that the G/ZnO NWs device exhibits great promise for highly efficient UV photodetectors.

Synthesis of ZnO nanorods on a flexible Phynox alloy substrate: influence of growth temperature on their properties

A novel flexible alloy substrate (Phynox, 50 mm thick) was used for the synthesis of zinc oxide (ZnO) nanorods via a low-temperature solution growth method. The growth of ZnO nanorods was observed over a low temperature range of 60-90 degrees C for a growth duration of 4 hours. The as-synthesized nanorods were characterized using field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) for their morphology, crystallinity, microstructure and composition. The as-grown ZnO nanorods were observed to be relatively vertical to the substrate. However, the morphology of the ZnO nanorods in terms of their length, diameter and aspect ratio was found to vary with the growth temperature. The morphological variation was mainly due to the effects of the various relative growth rates observed at the different growth temperatures. The growth temperature influenced ZnO nanorods were also analyzed for their wetting (either hydrophobic or hydrophilic) properties. After carrying out multiple wetting behaviour analyses, it has been found that the as-synthesized ZnO nanorods are hydrophobic in nature. The ZnO nanorods have potential application possibilities in self-cleaning devices, sensors and actuators as well as energy harvesters such as nanogenerators.

ZnO quantum dots and graphene based heterostructure for excellent photoelastic and highly sensitive ultraviolet photodetector

Heterostructures comprised of zinc oxide quantum dots (ZnO QDs) and graphene are presented for ultraviolet photodetectors (UV PD). Graphene-ZnO QDs-graphene (G-ZnO QDs-G) based PD demonstrated an excellent UV photoresponse with outstanding photoelastic characteristics when illuminated for several cycles with a periodicity 5 s. PD demonstrated faster detection ability with the response and recovery times of 0.29 s in response to much lower UV illumination. A direct variation in photoresponse is revealed with the bias voltage as well as UV illumination intensity. A drastic reduction in the dark current is noticed due to potential barrier formation between adjacent ZnO QDs and the recombination rate reduces by directly transferring photogenerated charge carriers from ZnO QDs to graphene for enhanced the charge mobility.

Origin of giant dielectric constant and conductivity behavior in Zn1-xMgxO (0 <= x <= 0.1) ceramics

Zn1-xMgxO ( <= x <= 0.1) ceramics were fabricated by conventional solid-state reaction of co-precipitated zinc oxide and magnesium hydroxide nanoparticles. Structural and morphological properties of the fabricated ceramics were studied using X-ray diffraction and scanning electron microscopic analysis. The dielectric measurements of the ceramics were carried out as a function of frequency and temperature respectively. Interestingly, Mg doped ZnO (MZO) samples exhibited colossal dielectric response (similar to 1 x 10(4) at 1 kHz) with Debye like relaxation. The detailed dielectric studies and thermal analyses showed that the unusual dielectric response of the samples were originated from the defected grain and grain boundary (GB) conductivity relaxations due to the absorbed atmospheric water vapor (moisture). Impedance spectroscopy was employed to determine the defected grain and GB resistances, capacitances and which supported Maxwell-Wagner type relaxation phenomena. (C) 2015 Elsevier Ltd. All rights reserved.

Instability in an amorphous In-Ga-Zn-O field effect transistor upon water exposure

The instability of an amorphous indium-gallium-zinc oxide (IGZO) field effect transistor is investigated upon water treatment. Electrical characteristics are measured before, immediately after and a few days after water treatment in ambient as well as in vacuum conditions. It is observed that after a few days of water exposure an IGZO field effect transistor (FET) shows relatively more stable behaviour as compared to before exposure. Transfer characteristics are found to shift negatively after immediate water exposure and in vacuum. More interestingly, after water exposure the off current is found to decrease by 1-2 orders of magnitude and remains stable even after 15 d of water exposure in ambient as well as in vacuum, whereas the on current more or less remains the same. An x-ray photoelectron spectroscopic study is carried out to investigate the qualitative and quantitative analysis of IGZO upon water exposure. The changes in the FET parameters are evaluated and attributed to the formation of excess oxygen vacancies and changes in the electronic structure of the IGZO bulk channel and at the IGZO/SiO2 interface, which can further lead to the formation of subgap states. An attempt is made to distinguish which parameters of the FET are affected by the changes in the electronic structure of the IGZO bulk channel and at the IGZO/SiO2 interface separately.

Sandwiched assembly of ZnO nanowires between graphene layers for a self-powered and fast responsive ultraviolet photodetector

A heterostructure of graphene and zinc oxide (ZnO) nanowires (NWs) is fabricated by sandwiching an array of ZnO NWs between two graphene layers for an ultraviolet (UV) photodetector. This unique structure allows NWs to be in direct contact with the graphene layers, minimizing the effect of the substrate or metal electrodes. In this device, graphene layers act as highly conducting electrodes with a high mobility of the generated charge carriers. An excellent sensitivity is demonstrated towards UV illumination, with a reversible photoresponse even for a short period of UV illumination. Response and recovery times of a few milliseconds demonstrated a much faster photoresponse than most of the conventional ZnO nanostructure-based photodetectors. It is shown that the generation of a built-in electric field between the interface of graphene and ZnO NWs effectively contributes to the separation of photogenerated electron-hole pairs for photocurrent generation without applying any external bias. Upon application of external bias voltage, the electric field further increases the drift velocity of photogenerated electrons by reducing the charge recombination rates, and results in an enhancement of the photocurrent. Therefore, the graphene-based heterostructure (G/ZnO NW/G) opens avenues to constructing a novel heterostructure with a combination of two functionally dissimilar materials.

Sandwiched assembly of ZnO nanowires between graphene layers for a self-powered and fast responsive ultraviolet photodetector

A heterostructure of graphene and zinc oxide (ZnO) nanowires (NWs) is fabricated by sandwiching an array of ZnO NWs between two graphene layers for an ultraviolet (UV) photodetector. This unique structure allows NWs to be in direct contact with the graphene layers, minimizing the effect of the substrate or metal electrodes. In this device, graphene layers act as highly conducting electrodes with a high mobility of the generated charge carriers. An excellent sensitivity is demonstrated towards UV illumination, with a reversible photoresponse even for a short period of UV illumination. Response and recovery times of a few milliseconds demonstrated a much faster photoresponse than most of the conventional ZnO nanostructure-based photodetectors. It is shown that the generation of a built-in electric field between the interface of graphene and ZnO NWs effectively contributes to the separation of photogenerated electron-hole pairs for photocurrent generation without applying any external bias. Upon application of external bias voltage, the electric field further increases the drift velocity of photogenerated electrons by reducing the charge recombination rates, and results in an enhancement of the photocurrent. Therefore, the graphene-based heterostructure (G/ZnO NW/G) opens avenues to constructing a novel heterostructure with a combination of two functionally dissimilar materials.