There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Antibacterial activity of zinc oxide nanoparticles (ZnO-NPs) has received significant interest worldwide particularly by the implementation of nanotechnology to synthesize particles in the nanometer region. Many microorganisms exist in the range from hundreds of nanometers to tens of micrometers. ZnO-NPs exhibit attractive antibacterial properties due to increased specific surface area as the reduced particle size leading to enhanced particle surface reactivity. ZnO is a bio-safe material that possesses photo-oxidizing and photocatalysis impacts on chemical and biological species. This review covered ZnO-NPs antibacterial activity including testing methods, impact of UV illumination, ZnO particle properties (size, concentration, morphology, and defects), particle surface modification, and minimum inhibitory concentration. Particular emphasize was given to bactericidal and bacteriostatic mechanisms with focus on generation of reactive oxygen species (ROS) including hydrogen peroxide (H2O2), OH− (hydroxyl radicals), and O2 −2 (peroxide). ROS has been a major factor for several mechanisms including cell wall damage due to ZnO-localized interaction, enhanced membrane permeability, internalization of NPs due to loss of proton motive force and uptake of toxic dissolved zinc ions. These have led to mitochondria weakness, intracellular outflow, and release in gene expression of oxidative stress which caused eventual cell growth inhibition and cell death. In some cases, enhanced antibacterial activity can be attributed to surface defects on ZnO abrasive surface texture. One functional application of the ZnO antibacterial bioactivity was discussed in food packaging industry where ZnO-NPs are used as an antibacterial agent toward foodborne diseases. Proper incorporation of ZnO-NPs into packaging materials can cause interaction with foodborne pathogens, thereby releasing NPs onto food surface where they come in contact with bad bacteria and cause the bacterial death and/or inhibition.

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Review on Zinc Oxide Nanoparticles: Antibacterial Activity and Toxicity Mechanism.

We present a review of current research on the optical properties of ZnO nanostructures. We provide a brief introduction to different fabrication methods for various ZnO nanostructures and some general guidelines on how fabrication parameters (temperature, vapor-phase versus solution-phase deposition, etc.) affect their properties. A detailed discussion of photoluminescence, both in the UV region and in the visible spectral range, is provided. In addition, different gain (excitonic versus electron hole plasma) and feedback (random lasing versus individual nanostructures functioning as Fabry-Perot resonators) mechanisms for achieving stimulated emission are described. The factors affecting the achievement of stimulated emission are discussed, and the results of time-resolved studies of stimulated emission are summarized. Then, results of nonlinear optical studies, such as second-harmonic generation, are presented. Optical properties of doped ZnO nanostructures are also discussed, along with a concluding outlook for research into the optical properties of ZnO.

Optical properties of ZnO nanostructures.

Gallium nitride (GaN) and its allied binaries InN and AIN as well as their ternary compounds have gained an unprecedented attention due to their wide-ranging applications encompassing green, blue, violet, and ultraviolet (UV) emitters and detectors (in photon ranges inaccessible by other semiconductors) and high-power amplifiers. However, even the best of the three binaries, GaN, contains many structural and point defects caused to a large extent by lattice and stacking mismatch with substrates. These defects notably affect the electrical and optical properties of the host material and can seriously degrade the performance and reliability of devices made based on these nitride semiconductors. Even though GaN broke the long-standing paradigm that high density of dislocations precludes acceptable device performance, point defects have taken the center stage as they exacerbate efforts to increase the efficiency of emitters, increase laser operation lifetime, and lead to anomalies in electronic devices. The p...

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Luminescence properties of defects in GaN

Light-Emitting Diodes. (Monographs in Electrical and Electronic Engineering.) By A. A. Bergh and P. J. Dean. Pp. viii+591. (Clarendon: Oxford; Oxford University: London, 1976.) £22.

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Light-emitting diodes

Nanometer sized whiskers (nanowires) offer a vehicle for the study of size-dependent phenomena. While quantum-size effects are commonly expected and easily predicted, size reduction also causes more atoms to be closer to the surface. Here we show that intensity relations of below-band-gap and band-edge luminescence in ZnO nanowires depend on the wire radius. Assuming a surface layer wherein the surface-recombination probability is 1 (surface-recombination approximation), we explain this size effect in terms of bulk-related to surface-related material-volume ratio that varies almost linearly with the radius. This relation supports a surface-recombination origin for the deep-level luminescence we observe. The weight of this surface-luminescence increases as the wire radius decreases at the expense of the band-edge emission. Using this model, we obtain a radius of 30 nm, below which in our wires surface-recombination prevails. More generally, our results suggest that in quantum-size nanowires, surface-recombination may entirely quench band-to-band recombination, presenting an efficient sink for charge carriers that unless deactivated may be detrimental for electronic devices.

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Size-dependent surface luminescence in ZnO nanowires

Photoconductivity is studied in individual ZnO nanowires. Under ultraviolet (UV) illumination, the induced photocurrents are observed to persist both in air and in vacuum. Their dependence on UV intensity in air is explained by means of photoinduced surface depletion depth decrease caused by oxygen desorption induced by photogenerated holes. The observed photoresponse is much greater in vacuum and proceeds beyond the air photoresponse at a much slower rate of increase. After reaching a maximum, it typically persists indefinitely, as long as good vacuum is maintained. Once vacuum is broken and air is let in, the photocurrent quickly decays down to the typical air-photoresponse values. The extra photoconductivity in vacuum is explained by desorption of adsorbed surface oxygen which is readily pumped out, followed by a further slower desorption of lattice oxygen, resulting in a Zn-rich surface of increased conductivity. The adsorption-desorption balance is fully recovered after the ZnO surface is exposed to air, which suggests that under UV illumination, the ZnO surface is actively "breathing" oxygen, a process that is further enhanced in nanowires by their high surface to volume ratio.

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Photoinduced oxygen release and persistent photoconductivity in ZnO nanowires

The deep level energy distribution associated with the well-known ‘‘yellow luminescence’’ in GaN is studied by means of two complementary deep level techniques: photoluminescence and surface photovoltage spectroscopy. The combined experimental results show that the yellow luminescence is due to capture of conduction band electrons, or electrons from shallow donors ~with a maximum depth on the order of the thermal energy! by a deep acceptor level with a broad energy distribution, centered at ;2.2 eV below the conduction band edge. In addition, the results show that the density of yellow luminescence related states possesses a significant surface component. @S0163-1829~99!16215-5#

Yellow luminescence and related deep levels in unintentionally doped GaN films

ZnO surfaces adsorb oxygen in the dark and emit CO2 when exposed to white light, reminiscent of the lungs of living creatures. We find that this exchange of oxygen with the ambient affects the integrity of the ZnO surface. Thus, it forms a basis for several interesting surface phenomena in ZnO, such as photoconductivity, photovoltage, and gas sensing, and has a role in ZnO electrical conduction. Using x-ray photoelectron spectroscopy on ZnO nanowires, we observed a decomposition of ZnO under white light and formation of oxygen-depleted surface, which explains photoconductivity by the electron donation of oxygen vacancies. Our findings suggest that the observed decomposition of the ZnO lattice may only take place due to photon-induced reduction of ZnO by carbon containing molecules (or carbo-photonic reduction), possibly from the ambient gas, accounting in a consistent way for both the reduced demands on the energy required for decomposition and for the observed emission of lattice oxygen in the form of CO2. The formation of oxygen-vacancy rich surface is suggested to induce surface delta doping, causing accumulation of electrons at the surface, which accounts for both the increase in conductivity and the flattening of the energy bands. Using surface photovoltage spectroscopy in ultra high vacuum, we monitored changes in the deep level spectrum. We observe a wide optical transition from a deep acceptor to the conduction band, which energy position coincides with the position of the so called “green luminescence” in ZnO. This green transition disappears with the formation of surface oxygen vacancies. Since the oxygen vacancies are donors, while the green transition involves surface acceptors, the results suggest that the initial emission of oxygen originates at the defect sites of the latter, thereby eliminating each other. This suggests that the green transition originates at surface Zn vacancy acceptors. Removing an oxygen atom from a Zn vacancy completes the vacancy to become a full ZnO molecule vacancy, which does not produce deep levels. Our results explain why ZnO finds use as an electrical detector for oxygen and for carbon containing gas molecules. They may also shed new light on photocatalytic uses of ZnO. It is suggested that similar surface phenomena may affect other semiconducting oxides.

Interaction of light with the ZnO surface: Photon induced oxygen "breathing," oxygen vacancies, persistent photoconductivity, and persistent photovoltage

Surface photovoltage spectroscopy, photoluminescence, Auger electron spectroscopy and x-ray photoelectron spectroscopy were used to correlate the chemical changes induced by HCl etching of GaN surface to changes in the yellow luminescence related states, through their manifestation in surface photovoltage. The results show a correlation between a removal of the gallium oxide from the surface and a reduction of the yellow luminescence related transition in the surface photovoltage spectra. Based on this observation, it is suggested that the well known yellow luminescence is emitted from surface states associated with the gallium oxide that decorates the free surface and possibly also the substrate interface and internal grain boundaries.

Ilan Shalish

Papers

Size-dependent surface luminescence in ZnO nanowires

Photoinduced oxygen release and persistent photoconductivity in ZnO nanowires

Yellow luminescence and related deep levels in unintentionally doped GaN films

Interaction of light with the ZnO surface: Photon induced oxygen "breathing," oxygen vacancies, persistent photoconductivity, and persistent photovoltage

Surface states and surface oxide in GaN layers