The effects of sub-bandgap transitions and the defect density of states on the photocurrent response of a single ZnO-coated silica nanospring.

The electrical and optoelectronic properties of nanometer-sized ZnO structures are highly influenced by its native point defects. Understanding and controlling these defects are essential for the development of high-performance ZnO-based devices. Here, an electrical device consisting of a polycrystalline ZnO-coated silica nanospring was fabricated and used to characterize the electrical and photoconductive properties of the ZnO layer using near-UV (405 nm) and sub-bandgap (532 and 633 nm) excitation sources. We observe a photocurrent response with all three wavelengths and notably with 532 nm green illumination, which is the energy associated with deep oxygen vacancies. The polycrystalline ZnO-coated silica nanospring exhibits a high responsivity of 1740 A W-1 with the 405 nm excitation source. Physical models are presented to describe the photocurrent rise and decay behavior of each excitation source where we suggest that the rise and decay characteristics are highly dependent on the energy of the excitation source and the trapping of electrons and holes in intermediate defect levels in the bandgap. The energy levels of the trap depths were determined from the photoconductive decay data and are matched to the reported energy levels of singly and doubly ionized oxygen vacancies. A phenomenological model to describe the dependence of the saturation photocurrent on excitation intensity is presented in order to understand the characteristics of the observed breaks in the slopes of the saturation photocurrent versus excitation intensity profile.

ZnO Microfiltration Membranes for Desalination by a Vacuum Flow-Through Evaporation Method.

ZnO was deposited on macroporous α-alumina membranes via atomic layer deposition (ALD) to improve water flux by increasing their hydrophilicity and reducing mass transfer resistance through membrane pore channels. The deposition of ZnO was systemically performed for 4-128 cycles of ALD at 170 °C. Analysis of membrane surface by contact angles (CA) measurements revealed that the hydrophilicity of the ZnO ALD membrane was enhanced with increasing the number of ALD cycles. It was observed that a vacuum-assisted 'flow-through' evaporation method had significantly higher efficacy in comparison to conventional desalination methods. By using the vacuum-assisted 'flow-through' technique, the water flux of the ZnO ALD membrane (~170 L m-2 h-1) was obtained, which is higher than uncoated pristine membranes (92 L m-2 h-1). It was also found that ZnO ALD membranes substantially improved water flux while keeping excellent salt rejection rate (>99.9%). Ultrasonic membrane cleaning had considerable effect on reducing the membrane fouling.

Luminescent properties of a 3,5-diphenylpyrazole bridged Pt(ii) dimer.

We report the synthesis, electrochemistry, photophysical properties and electroluminescence of a highly luminescent pyrazolate-bridged platinum(ii) complex. The complex has the general formula of [((N^C^N)Pt)2(µ-pz)][PF6] where N^C^N = 1,3-di(2-pyridyl)benzene and µ-pz = 3,5-diphenylpyrazolate. The X-ray structure shows that the bridging pyrazolate ligand causes a close Pt-Pt interaction of 3.05(7) Å. The emission profile of the complex was determined in solution, glassy 2-methyltetrahydrofurane at 77 K, and the solid state at both room temperature and 77 K. Each emission profile displayed a strong red metal-metal-to-ligand charge transfer while the solution and glassy 2-methyltetrahydrofurane emission profiles also displayed a ligand-centred transition. The absolute quantum yields of the complex in solution and the solid state at room temperate are 86% and 39%, respectively. Light-emitting electrochemical cells (LEECs) of [((N^C^N)Pt)2(µ-pz)][PF6] were fabricated which displayed appreciable electroluminescence, among the brightest and most efficient LEECs from dinuclear compounds to date.

Electrical characterization of ZnO-coated nanospring ensemble by impedance spectroscopy: probing the effect of thermal annealing.

The effects of thermal annealing on the electrical properties of randomly oriented ZnO-coated nanospring ensembles were extensively investigated through AC impedance spectroscopy. Annealing the nanospring mats for an hour at 873 K in air showed significant change in ZnO morphology, reduced electrical conductivity due to the presence of grain boundaries, decreased apparent donor concentration, and faster decay of sub-band gap photocurrent. The role of the nanospring-nanospring junctions in the conduction of carriers in the ensemble was also examined, as well as evaluation of their responsiveness to thermal and optical stimulations. This work identifies the effects of heat treatment in the presence of air on the electrical properties of the nanospring ensembles, which are related to the mesoscopic morphology and interconnect within the ensemble and the properties of the ZnO coating.

The Effect of UV Illumination on the Room Temperature Detection of Vaporized Ammonium Nitrate by a ZnO Coated Nanospring-Based Sensor.

The effect of UV illumination on the room temperature electrical detection of ammonium nitrate vapor was examined. The sensor consists of a self-assembled ensemble of silica nanosprings coated with zinc oxide. UV illumination mitigates the baseline drift of the resistance relative to operation under dark conditions. It also lowers the baseline resistance of the sensor by 25% compared to dark conditions. At high ammonium nitrate concentrations (120 ppm), the recovery time after exposure is virtually identical with or without UV illumination. At low ammonium nitrate concentrations (20 ppm), UV illumination assists with refreshing of the sensor by stimulating analyte desorption, thereby enabling the sensor to return to its baseline resistance. Under dark conditions and low ammonium nitrate concentrations, residual analyte builds up with each exposure, which inhibits the sensor from returning to its original baseline resistance and subsequently impedes sensing due to permanent occupation of absorption sites.

Emergent Electrical Properties of Ensembles of 1D Nanostructures and Their Impact on Room Temperature Electrical Sensing of Ammonium Nitrate Vapor.

Ammonium nitrate is an explosive agent that has a very low vapor pressure, which makes airborne detection very challenging. Detection of ammonium nitrate vapor has been achieved by using silica nanospring mats coated with a thin semiconducting layer of zinc oxide. The sensor was operated at room temperature and under ambient conditions in air. Lock-in amplification was employed to measure the change in electrical resistance of the sensor upon exposure to the said target gas analyte. The sensor showed fast detection, only taking ∼15 s to reach its peak response, and exhibited a moderate recovery time of approximately 0.5 min/20 ppm for <40 ppm exposures. A comparison between the ZnO coated nanospring sensor and ZnO thin film sensor demonstrated that the nanospring sensor has superior sensitivity and responsiveness over the thin film sensor. A percolation-based model is proposed to explain the greater sensitivity at low analyte concentrations of the ZnO-nanospring sensor, as compared to a ZnO thin film sensor.

The Effect of the Dielectric Constant and Ion Mobility in Light-Emitting Electrochemical Cells.

Light-emitting electrochemical cells (LEECs) are a promising low-cost option for display and solid-state lighting. In these devices, the interplay of mobile ions, electrons, and holes makes for rich physics that can be leveraged for high performance. One example of this interplay is in the formation and radiative decay of excitons-bound electron and hole pairs. Considerations from exciton binding and Langevin recombination suggest that a low dielectric constant (ϵ) would enhance emission. However, emission is also enhanced by the product of the bulk hole and electron concentrations, which in LEECs are enhanced by the motion of small mobile ions yielding high dielectric constants. These competing effects make it difficult to predict whether active layers with low or high dielectric constants will optimize device performance. Here, the effect of varying the dielectric constant on the performance of LEEC devices from ionic transition-metal complexes was studied by systematically exchanging the negative counterions paired with an iridium complex emitter. Electrochemical impedance spectroscopy, constant voltage and constant current device studies, and drift-diffusion simulations were performed. The results clarify the competing effects of Langevin bimolecular recombination and ion-assisted injection processes occurring in LEECs.

Phenyl substitution of cationic bis-cyclometalated iridium(iii) complexes for iTMC-LEECs.

A series of seven cationic bis-cyclometalated iridium(iii) complexes of the form [(C^N)2(N^N)Ir][PF6] has been designed in order to examine the effect of bulky, hydrophobic phenyl substituents on the structure-property relationship of these ionic transition metal complexes (iTMCs) in light-emitting electrochemical cells (LEECs). Capping phenyl substituents on the cyclometalating and ancillary ligands allows for individual tuning of the HOMO and LUMO energy levels, respectively, yielding an emission range from yellow to red. The complexes in this series exhibit increased quantum yields, up to 70% higher than the unoptimized, archetypal [(2-phenylpyridine)2(2,2'-bipyridine)Ir][PF6]. Among these, one complex, C3, was recently reported to produce devices with superior luminance and efficiency. Simultaneous measure of the series of complexes enabled the clear discernment of trends in device performance connected to fundamental structure-property relationships that elucidate the origin of enhanced luminance. In general, phenyl substitution of the 2-phenylpyridine ligands of the parent complex produced higher luminance and faster device response than phenyl substitution of the 2,2'-bipyridine ligand. Overall, complex design and device engineering produce competitive LEECs from simple, single-layer architectures. The synthesis, crystallographic, photophysical, and electrochemical properties of the iTMCs, along with the electroluminescence properties of the LEEC devices are reported herein.

Discerning the Impact of a Lithium Salt Additive in Thin-Film Light-Emitting Electrochemical Cells with Electrochemical Impedance Spectroscopy.

Light-emitting electrochemical cells (LEECs) from small molecules, such as iridium complexes, have great potential as low-cost emissive devices. In these devices, ions rearrange during operation to facilitate carrier injection, bringing about efficient operation from simple, single-layer devices. Prior work has shown that the luminance, efficiency, and responsiveness of iridium LEECs is greatly enhanced by the inclusion of small fractions of lithium salts, but much remains to be understood about the origin of this enhancement. Recent work with planar devices demonstrates that lithium additives in iridium LEECs enhance double-layer formation. However, the quantitative influence of lithium salts on the underlying physics of conventional thin-film, sandwich structure LEECs, which beneficially operate at low voltages and generate higher luminance, has yet to be clarified. Here, we use electrochemical impedance spectroscopy to discern the impact of the lithium salt concentration on double-layer formation within the device and draw correlations with performance metrics, such as current, luminance, and external quantum efficiency.

Influence of Lithium Additives in Small Molecule Light-Emitting Electrochemical Cells.

Light-emitting electrochemical cells (LEECs) utilizing small molecule emitters such as iridium complexes have great potential as low-cost emissive devices. In these devices, ions rearrange during operation to facilitate carrier injection, bringing about efficient operation from simple, single layer devices. Recent work has shown that the luminance, efficiency, and responsiveness of iridium-based LEECs are greatly enhanced by the inclusion of small amounts of lithium salts (≤0.5%/wt) into the active layer. However, the origin of this enhancement has yet to be demonstrated experimentally. Furthermore, although iridium-based devices have been the longstanding leader among small molecule LEECs, fundamental understanding of the ionic distribution in these devices under operation is lacking. Herein, we use scanning Kelvin probe microscopy to measure the in situ potential profiles and electric field distributions of planar iridium-based LEECs and clarify the role of ionic lithium additives. In pristine devices, it is found that ions do not pack densely at the cathode, and ionic redistribution is slow. Inclusion of small amounts of Li[PF6] greatly increases ionic space charge near the cathode that doubles the peak electric fields and enhances electronic injection relative to pristine devices. This study confirms and clarifies a number of longstanding hypotheses regarding iridium LEECs and recent postulates concerning optimization of their operation.

Enhanced Luminance of Electrochemical Cells with a Rationally Designed Ionic Iridium Complex and an Ionic Additive.

Light-emitting electrochemical cells (LEECs) offer the potential for high efficiency operation from an inexpensive device. However, long turn-on times and low luminance under steady-state operation are longstanding LEEC issues. Here, we present a single-layer LEEC with a custom-designed iridium(III) complex and a lithium salt additive for enhanced device performance. These devices display reduced response times, modest lifetimes, and peak luminances as high as 5500 cd/m(2), 80% higher than a comparable device from an unoptimized complex and 50% higher than the salt-free device. Improved device efficiency suggests that salt addition balances space charge effects at the interfaces. Extrapolation suggests favorable half-lives of 120 ± 10 h at 1000 cd/m(2) and 3800 ± 400 h at 100 cd/m(2). Overall, complex design and device engineering produce competitive LEECs from simple, single-layer architectures.