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.

/pdf/review-on-zinc-oxide-nanoparticles-antibacterial-activity-2smaigi8sc.pdf

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

A phototransistor based on a chemical vapor deposited (CVD) MoS2 monolayer exhibits a high photoresponsivity (2200 A W(-1) ) and an excellent photogain (5000). The presence of shallow traps contributes to the persistent photoconductivity. Ambient adsorbates act as p-dopants to MoS2 , decreasing the carrier mobility, photoresponsivity, and photogain.

High-gain phototransistors based on a CVD MoS₂ monolayer.

ZnO is a material which is of great interest for a variety of applications due to its unique properties and the availability of a variety of growth methods resulting in a number of different morphologies and a wide range of material properties of synthesized nanostructures. In this review, we will discuss recent advances in important and/or controversial issues concerning ZnO properties and its applications. We will also discuss areas where further improvements are needed, and in particular discuss the issues related to the environmental stability of ZnO and its implications on reproducibility of measurements and the toxicity of ZnO nanomaterials.

ZnO nanostructures: growth, properties and applications

Due to its significant applications in many relevant fields, light detection in the solar-blind deep-ultraviolet (DUV) wavelength region is a subject of great interest for both scientific and industrial communities. The rapid advances in preparing high-quality ultrawide-bandgap (UWBG) semiconductors have enabled the realization of various high-performance DUV photodetectors (DUVPDs) with different geometries, which provide an avenue for circumventing numerous disadvantages in traditional DUV detectors. This article presents a comprehensive review of the applications of inorganic UWBG semiconductors for solar-blind DUV light detection in the past several decades. Different kinds of DUVPDs, which are based on varied UWBG semiconductors including Ga2O3, MgxZn1−xO, III-nitride compounds (AlxGa1−xN/AlN and BN), diamond, etc., and operate on different working principles, are introduced and discussed systematically. Some emerging techniques to optimize device performance are addressed as well. Finally, the existing techniques are summarized and future challenges are proposed in order to shed light on development in this critical research field.

Recent Progress in Solar-Blind Deep-Ultraviolet Photodetectors Based on Inorganic Ultrawide Bandgap Semiconductors

Germanium nanowires with p- and n-dopants were synthesized by chemical vapor deposition and used to construct complementary field effect transistors . Electrical transport and x-ray photoelectron spectroscopy data are correlated to glean the effects of Ge surface chemistry to the electrical characteristics of GeNWs. Large hysteresis due to water molecules strongly bound to GeO2 on GeNWs is revealed. Different oxidation behavior and hysteresis characteristics and opposite band bending due to Fermi level pinning by interface states between Ge and surface oxides are observed for p- and n-type GeNWs. Vacuum annealing above 400C is used to remove surface oxides and eliminate hysteresis in GeNW FETs. High-k dielectric HfO2 films grown on clean GeNW surfaces by atomic layer deposition (ALD) using an alkylamide precursor is effective serving as the first layer of surface passivation. Lastly, the depletion length along the radial direction of nanowires is evaluated. The result suggests that surface effects could be dominant over the bulk properties of small diameter wires.

https://arxiv.org/pdf/cond-mat/0407186.pdf

Surface Chemistry and Electrical Properties of Germanium 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.

/pdf/photoinduced-oxygen-release-and-persistent-photoconductivity-4x8riley6g.pdf

Photoinduced oxygen release and persistent photoconductivity in ZnO nanowires

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

The ability to control conductivity in semiconductor nanostructures is often challenged by surface states trapping the majority of the charge carriers. Addressing this challenge requires a reliable method for assessing electrical properties such as carrier concentration and mobility. Unfortunately, here we are facing another challenge, as the Hall effect is geometrically inapplicable to nanowires while the field effect model is also challenged by the geometry of the common nanowire field effect transistor, and can only yield channel mobility which is very different from Hall mobility. In this paper, we propose a method that combines resistivity and photovoltage measurements with a chemical perturbation to the surface to measure carrier concentration and mobility, as a function of wire diameter, and also to measure the surface state density and the surface band bending before and after the chemical treatment. We apply this method to CVD grown GaN nanowires, before and after a mild HCl etch. Using transmission electron microscope and x-ray photoelectron spectrometry we find that HCl removes the native gallium oxide. The etch is found to reduce the surface state density from 1 × 1012 to 5.3 × 1011 cm2, which is calculated from a reduction of the critical radius for full depletion from 7.6 to 4 nm, and a reduction of the surface band bending from 0.53 to 0.29 eV, observed using surface photovoltage. On the average, the values of carrier concentration we obtain are about ten times smaller, and the mobility about ten times greater, than values obtained using field effect transistors. Interestingly, the weak size dependence of the mobility disappears after etching, suggesting a causal linkage between the as-grown size dependence of the mobility and the density of surface states. The proposed method provides an experimental handle to the study of surface states and their effects on the electrical properties of nanowires.

Method for electrical characterization of nanowires.

A wurtzite GaAs epilayer grown on a zincblende GaAs substrate by metalorganic chemical vapor deposition is studied by surface photovoltage spectroscopy. The wurtzite structure of the epilayer is disclosed by scanning electron microscope images of surface pits, where the pits are seen to change their structure from a rectangular into a hexagonal shape. The wurtzite phase is also revealed in x-ray diffraction showing a 〈0002〉 diffraction alongside the main (200) diffraction, suggesting a “c” lattice constant of 0.668 nm. A comparison of room temperature surface photovoltage spectra taken from the epilayer sample and from an epilayer-etched substrate suggests a type II heterostructure with valence band difference of about 15 meV and bandgap difference of about 70 meV between the zincblende and the wurtzite GaAs polytypes.

Bandgap and band discontinuity in wurtzite/zincblende GaAs homomaterial heterostructure

Gold is commonly used nowadays in metal contacts to nanowire devices. Due to their small size, nanowire devices often get heat up enough to cause a reaction of the contact and substrate, whether during operation or as a result of a spontaneous pulse of an electrostatic discharge. In most cases, the point of failure is the metallization, as is the case studied here. Gold is useful not only for its good electrical conductance but also because it is a good heat conductor and inert to the ambient. To improve the survivability of a gold metallization for nanowire devices incorporating ZnO nanowire atop a SiC substrate, we used a sputter-deposited Ti-Si-N ternary diffusion barrier layer and a Ti adhesion layer between the top gold layer and a 4H-SiC substrate that survives 30 min of vacuum annealing at 850 °C and 5 days of annealing at 500 °C in Ar. Rutherford backscattering spectrometry and x-ray photoelectron spectroscopy were used to test the integrity of the layers before and after annealing both with and w...

Ron Gurwitz

Papers

Photoinduced oxygen release and persistent photoconductivity in ZnO nanowires

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

Method for electrical characterization of nanowires.

Bandgap and band discontinuity in wurtzite/zincblende GaAs homomaterial heterostructure

High-temperature gold metallization for ZnO nanowire device on a SiC substrate