https://chemistry.beloit.edu/classes/nanotech/ZnO/mattoday10_05_40.pdf

ZnO - nanostructures, defects, and devices

High concentrations of defects are introduced into nanoscale ZnO through non-equilibrium processes and resultant blue emissions are comprehensively analyzed, focusing on defect origins and broad controls. Some ZnO nanoparticles exhibit very strong blue emissions, the intensity of which first increase and then decrease with annealing. These visible emissions exhibit strong and interesting excitation dependences: 1) the optimal excitation energy for blue emissions is near the bandgap energy, but the effective excitation can obviously be lower, even 420 nm (2.95 eV < Eg = 3.26 eV); in contrast, green emissions can be excited only by energies larger than the bandgap energy; and, 2) there are several fixed emitting wavelengths at 415, 440, 455 and 488 nm in the blue wave band, which exhibit considerable stability in different excitation and annealing conditions. Mechanisms for blue emissions from ZnO are proposed with interstitial-zinc-related defect levels as initial states. EPR spectra reveal the predominance of interstitial zinc in as-prepared samples, and the evolutions of coexisting interstitial zinc and oxygen vacancies with annealing. Furthermore, good controllability of visible emissions is achieved, including the co-emission of blue and green emissions and peak adjustment from blue to yellow.

/pdf/blue-luminescence-of-zno-nanoparticles-based-on-non-1rinmcderc.pdf

Blue Luminescence of ZnO Nanoparticles Based on Non‐Equilibrium Processes: Defect Origins and Emission Controls

A novel amorphous oxide applicable, for example, to an active layer of a TFT is provided. The amorphous oxide comprises microcrystals.

Amorphous oxide and field effect transistor

Humidity measurement is one of the most significant issues in various areas of applications such as instrumentation, automated systems, agriculture, climatology and GIS. Numerous sorts of humidity sensors fabricated and developed for industrial and laboratory applications are reviewed and presented in this article. The survey frequently concentrates on the RH sensors based upon their organic and inorganic functional materials, e.g., porous ceramics (semiconductors), polymers, ceramic/polymer and electrolytes, as well as conduction mechanism and fabrication technologies. A significant aim of this review is to provide a distinct categorization pursuant to state of the art humidity sensor types, principles of work, sensing substances, transduction mechanisms, and production technologies. Furthermore, performance characteristics of the different humidity sensors such as electrical and statistical data will be detailed and gives an added value to the report. By comparison of overall prospects of the sensors it was revealed that there are still drawbacks as to efficiency of sensing elements and conduction values. The flexibility offered by thick film and thin film processes either in the preparation of materials or in the choice of shape and size of the sensor structure provides advantages over other technologies. These ceramic sensors show faster response than other types.

/pdf/humidity-sensors-principle-mechanism-and-fabrication-q8mq7scozc.pdf

Humidity Sensors Principle, Mechanism, and Fabrication Technologies: A Comprehensive Review

The Kirkendall effect is a consequence of the different diffusivities of atoms in a diffusion couple causing a supersaturation of lattice vacancies. This supersaturation may lead to a condensation of extra vacancies in the form of so-called “Kirkendall voids” close to the interface. On the macroscopic and micrometer scale these Kirkendall voids are generally considered as a nuisance because they deteriorate the properties of the interface. In contrast, in the nanoworld the Kirkendall effect has been positively used as a new fabrication route to designed hollow nano-objects. In this Review we summarize and discuss the demonstrated examples of hollow nanoparticles and nanotubes induced by the Kirkendall effect. Merits of this route are compared with other general methods for nanotube fabrication. Theories of the kinetics and thermodynamics are also reviewed and evaluated in terms of their relevance to experiments. Moreover, nanotube fabrication by solid-state reactions and non-Kirkendall type diffusion processes are covered.

/pdf/formation-of-nanotubes-and-hollow-nanoparticles-based-on-8yxfpqf0n3.pdf

Formation of nanotubes and hollow nanoparticles based on Kirkendall and diffusion processes: a review.

Undoped and Mn-doped ZnO samples were sintered at 1373, 1473, and 1573 K, for 2 h, in air, and then quenched to room temperature. Defect concentrations in these samples at the sintering temperatures and at room temperature and below were calculated using a refined defect model. Using the calculated electron concentrations and assuming a constant electron mobility of 100 cm2/Vs, conductivities at room temperature were calculated and compared with experimental ones. The agreement between the experimental and calculated conductivities is very good for all the samples of undoped and Mn-doped ZnO. In the Mn-doped ZnO case, the ionisation energy of the Mn defect in ZnO was estimated to be ∼2.0 eV. Using the experimental conductivities and the calculated electron concentrations, the electron mobilities were calculated between 70 and 300 K. The results show that the temperature dependence of the mobility in undoped ZnO is similar to that in ZnO single crystals observed in other works, and heavy Mn doping significantly reduces the electron mobility below room temperature probably due to impurity scattering. The role of Mn on the electrical conductivity of ZnO could be understood.

Defect chemistry and electrical characteristics of undoped and Mn-doped ZnO

Samples of Al-doped and Mn-doped ZnO with a doping level up to 1.2 mol% were sintered at temperatures from 1100 to 1400°C in air. dc Electrical conductivities of these samples at room temperature and below were measured, and the effects of the doping type, the doping level, the sintering temperature and time on the electrical conductivity of ZnO were investigated. It was found that Al increased the electrical conductivity of ZnO resulting in a manifestation of a metallic electrical conduction behaviour, and a semiconductor-metal transition occured in the Al-doped ZnO samples. For Mn-doped ZnO samples quenched from the sintering temperatures, the electrical conductivity decreased with the increase in the Mn content, but the samples still showed a semiconductor electrical conduction behaviour. In this way, one could obtain a systematic variation of the ZnO electrical conductivity from the high conductivity, Al-doped case, to the high resistivity, Mn-doped one, spanning over eight orders of magnitude, which is explained in the present communication.

Effect of Al and Mn doping on the electrical conductivity of ZnO

In PZT ceramics it is commonly observed that the tetragonal and the rhombohedral phases may coexist around the morphotropic phase boundary (MPB). Some controversy still exists concerning the causes of the real occurrence of the phase coexistence, the distribution of the coexisting phases and their chemical and structural properties. In a previous work we found a relation between the width of the coexistence region and the grain size of the ceramic that could be explained by the statistical distribution model, as long as the elementary phase volumes were considered as the ferroelectric domains inside the grain. In the present work the structural parameters of the phases and the dielectric permittivity of PZT in a compositional range covering the phase coexistence region are determined and analysed. It is observed that in both tetragonal and rhombohedral phases the permittivity increases as the lattice distortion relative to the cubic symmetry decreases. The dielectric permittivities of PZT inside the phase coexistence region were calculated considering that the phase coexistence corresponds to a statistical distribution of phases with the same composition. This model provides dielectric results consistent with the experimental ones. It was also shown that the maximum of the dielectric properties in the MPB does not result from the phase coexistence, but it is a consequence of the approach to a minimum structure distortion.

Phase coexistence region and dielectric properties of PZT ceramics

The densification and grain growth of ZnO doped with Al from 0.08 to 1.2 mol% were investigated during isothermal sintering between 1100 and 1400 °C. The Al dopant significantly inhibited the grain growth of ZnO and increased the grain growth exponent from 3 for pure ZnO to 4–6 for Al-doped ZnO. The grain growth activation energy was also changed from approximately 200 kJ/mol for pure ZnO to approximately 480 kJ/mol for Al-doped ZnO. The results of x-ray diffraction, scanning electron microscopy, and transmission electron microscopy showed that a ZnAl2O4 spinel phase existed as a second phase at the ZnO grain boundaries in Al-doped ZnO specimens. The spinel particles exerted an effective drag (pinning) on the migration of ZnO grain boundaries. The analyses of the Al doping effect on the densification rate provided evidence that the driving force for densification was reduced by the second-phase particles. A mechanism of pore surface drag (pinning) on densification equivalent to the observed drag (pinning) of grain boundaries on grain growth was proposed.

Densification and grain growth of Al-doped ZnO

The Debye model is frequently used to explain the dielectric behaviour of materials. A good description of the experimental results is often obtained by using a distribution of relaxation times. In this work, it is proposed to extend the Debye model to the depolarisation of two or more types of dipoles occurring simultaneously. With this procedure, it is observed that permittivity Cole–Cole plots appear with two or more semicircles overlapping each other, and can give origin to one flattened semicircle. The same type of behaviour is observed for the impedance Cole–Cole plots, and both type of description of experimental data usually give very similar results. Assuming that relaxation times are thermally activated parameters, with positive or negative activation energies depending on the type of the dipoles, it is possible to obtain dielectric responses similar to those of the paraelectric regions of ferroelectric materials, and dielectric peaks on the permittivity-versus-temperature graphs similar to the relaxor behaviour found in some ferroelectric materials. ©

Pedro Q. Mantas

Papers

Defect chemistry and electrical characteristics of undoped and Mn-doped ZnO

Effect of Al and Mn doping on the electrical conductivity of ZnO

Phase coexistence region and dielectric properties of PZT ceramics

Densification and grain growth of Al-doped ZnO

Dielectric response of materials: extension to the Debye model