ZnS nanostructures: From synthesis to applications

CuO nanostructures: Synthesis, characterization, growth mechanisms, fundamental properties, and applications

CeO2 is a catalytic material of exceptional technological importance, and the precise role of oxygen vacancies is crucial to the greater understanding of these oxide materials. In this work, two ceria nanorod samples with different types and distributions of oxygen vacancies were synthesized. A direct relationship between the concentration of the larger size oxygen vacancy clusters and the reducibility/reactivity of nanosized ceria was revealed. These results may be an important step in understanding and designing active sites at the surface of metal oxide catalytic materials.

Oxygen Vacancy Clusters Promoting Reducibility and Activity of Ceria Nanorods

ZnO nanostructures for optoelectronics: Material properties and device applications

TiO2 nanocrystals with tunable bulk/surface defects were synthesized and characterized with TEM, XRD, BET, positron annihilation, and photocurrent measurements. The effect of defects on photocatalytic activity was studied. It was found for the first time that decreasing the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals could significantly improve the separation efficiency of photogenerated electrons and holes, thus significantly enhancing the photocatalytic efficiency.

Tuning the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals leads to high photocatalytic efficiency.

Role of defects in tailoring structural, electrical and optical properties of ZnO

Mechanical milling and subsequent annealing in air at temperatures between 210 and 1200°C have been carried out on high purity ZnO powder to study the defect generation and recovery in the material. Lowering of average grain size (from 76±1to22±0.5nm) as a result of milling has been estimated from the broadening of x-ray lines. Substantial grain growth in the milled sample occurs above 425°C annealing temperature. Positron annihilation lifetime (PAL) analysis of the samples shows a distinct decrease of the average lifetime of positrons very near the same temperature zone. As indicated from both x-ray diffraction (XRD) and PAL results, high temperature (>700°C) annealed samples have a better crystallinity (or lower defect concentration) than even the nonmilled ZnO. In contrast, the measured optical band gap of the samples (from absorption spectroscopy) does not confirm lowering of defects with high temperature annealing. Thermally generated defects at oxygen sites cause significant modification of the optical absorption; however, they are not efficient traps for positrons. Different thermal stages of generation and recovery of cationic as well as anionic defects in granular ZnO are discussed in the light of XRD, PAL, and optical absorption studies.

Annealing effect on nano-ZnO powder studied from positron lifetime and optical absorption spectroscopy

The correlation between the structural and optical properties of mechanically milled high purity ZnO powder is reported in the present work. Reduction of average grain size and enhancement of strain as a result of milling have been estimated from the broadening of x-ray powder diffraction patterns. After milling, the optical bandgap, revealed from absorption spectroscopy, has been red-shifted and the width of the localized states, calculated from the analysis of the Urbach tail below the absorption edge, has been extended more and more into the bandgap. Moreover, the band tailing parameter is seen to vary exponentially with the inverse of the grain size. Finally, the positron annihilation technique has been employed to identify the nature of defects present (or generated due to milling) in the system and thereby to correlate the defect mediated modification of optical absorption in ZnO.

Defects and the optical absorption in nanocrystalline ZnO

As-supplied polycrystalline ZnO samples (purity 99.9% from Sigma-Aldrich, Germany) have been annealed at different temperatures and subsequently characterized by positron annihilation spectroscopy, x-ray-diffraction (XRD) analysis, thermogravimetric analysis (TGA), and resistivity measurements. Positron annihilation lifetime analysis and coincidence Doppler-broadened electron-positron annihilation γ-radiation (CDBEPAR) line-shape measurements have been employed at a time to identify the nature of defects in differently annealed ZnO materials. Annealing up to 300°C, an increase of defect lifetime (τ2) as well as shape parameter (S parameter) has been observed. Further annealing causes a large decrease of τ2 and S parameter. TGA study shows considerable mass loss from ZnO as the annealing temperature is increased above 300°C. This is possibly due to oxygen evaporation from the sample. The c-axis lattice parameter, extracted from the XRD spectra, shows an increase due to annealing above 600°C, which is a sig...

Defect dynamics in annealed ZnO by positron annihilation spectroscopy

Different samples of Zn1−xMnxO series have been prepared using conventional solid-state sintering method. We identified up to what extent doping will enable us to synthesize single-phase polycrystalline Mn-doped ZnO sample, which is one of the prerequisites for dilute magnetic semiconductor, and we have analyzed its some other physical aspects. In synthesizing the samples, proportion of Mn varies from 1 to 5 at%. However, the milling time varied (6, 12, 24, 48 and 96 h) only for 2 at% Mn-doped samples while for other samples (1, 3, 4 and 5 at% Mn doped) the milling time has been fixed to 96 h. Room-temperature X-ray diffraction (XRD) data reveal that all of the prepared samples up to 3 at% of Mn doping exhibit wurtzite-type structure, and no segregation of Mn and/or its oxides has been found. The 4 at% Mn-doped samples show a weak peak of ZnMn2O4 apart from the other usual peaks of ZnO and the intensity of this impurity peak has been further increased for 5 at% of Mn doping. So beyond 3 at% doping, single-phase behavior is destroyed. Band gap for all the 2 at% Mn-doped samples has been estimated to be between 3.21 and 3.19 eV and the reason for this low band gap values has been explained through the grain boundary trapping model. The room-temperature resistivity measurement shows an increase of resistivity up to 48 h of milling and with further milling it saturates. The defect state of these samples has been investigated using the positron annihilation lifetime (PAL) spectroscopy technique. Here all the relevant lifetime parameters of positron i.e. free annihilation (τ1) at defect site (τ2) and average (τav) increases with milling time.

Sreetama Dutta

Papers

Role of defects in tailoring structural, electrical and optical properties of ZnO

Annealing effect on nano-ZnO powder studied from positron lifetime and optical absorption spectroscopy

Defects and the optical absorption in nanocrystalline ZnO

Defect dynamics in annealed ZnO by positron annihilation spectroscopy

Synthesis and characterization of single-phase Mn-doped ZnO