Piezoelectric hard/soft effects of multivalence co-dopants (Sb and Mn) in correlation with their location in the lattice, were investigated in PZT ceramics, prepared by conventional ceramic technology, with the following compositions: Pb0.98Sr0.02 ((Ti0.49Zr0.51)(1-0.015-x)Mn0.015Sbx)O-3 with x = 0, 0.005, 0.01, 0.02, 0.03, where antimony was initially assumed to substitute for Ti/Zr ions. The antimony valence state was found to be +3 in all samples by X-ray Photoelectron Spectroscopy investigations. The Electron Paramagnetic Resonance spectra evidenced a steep enhancement of the Mn2+ concentration upon increasing antimony doping level, explained by a charge compensation mechanism, between the Sb3+ ions substituting Pb2+ at the A-sites and the Mn2+ ions, localized at the B-sites. The incorporation of Sb3+ at the A-site of the PZT lattice is also supported by the variation of the lattice parameters, determined by X-ray Diffraction, with the increasing Sb concentration. The investigation of the dielectric, electromechanical and ferroelectric properties evidenced a hard piezoelectric behavior, mainly attributed to the presence of large sized Mn2+ ions, localized at B-sites. Our results prove that the piezoelectric hard/soft response is decisively influenced by the interplay between multiple valence states and locations of the co-dopants, on one hand, and the charge compensation mechanisms, on the other hand. This provides indirect information about the location of some co-dopants which can substitute for both cationic sites in the PZT based ceramics.

In this paper, we investigate the origin of point defects revealed by electron spin resonance (ESR) and photoluminescence (PL) emission in correlation with the photocatalytic activity of ZnO nanocrystals subjected to thermal annealing at various temperatures. Two ESR signals at g similar to 1.96 and similar to 2.003 were consistently observed in all annealed ZnO samples. However, their relative intensities have changed, indicating that the point defect densities were influenced by the annealing temperature. Interestingly, when doping nanoZnO with Cr3+, the Q-band ESR measurements at T = 100 K did show that the g similar to 1.96 signal was completely passivated, suggesting that the origin of the signal lies in the electrons located near the conduction band, i.e. at a shallow-donor level. The intensity of the g similar to 2.003 signal decreased by rising the annealing temperature, and this is attributed to the depopulation of zinc interstitials through the thermally induced migration process and/or recombination with the zinc vacancies. The green PL emission line at similar to 520 nm, which is dominant in the 700 degrees C annealed ZnO sample, shows a correlation with the ESR signal at g similar to 1.96, whose origin is attributed to the radiative transition of the electron from the shallow donor level to the singly ionized zinc vacancy. Furthermore, the high density of the shallow donor electron states was found to be primarily responsible for the high photocatalytic activity in the degradation of methylene blue.

A versatile, modular in situ high-intensity monochromatic illumination set-up installed on a standard Q-band ESR spectrometer equipped with a cryostat and probe head for measurements at cryogenic temperatures, which can be easily assembled from commercially available optical components is presented. Using as monochromatic light sources pig-tailed laser diodes (LDs) or fiber-coupled light-emitting diodes (LEDs), a high efficiency of the light transfer (more than 95%) through an optical guide inserted in the sample holder is achieved in the sample area of the microwave cavity. With various LEDs and LDs, one can perform ESR in situ illumination experiments from UV to far-IR, in both cw and pulse mode. Its operation is illustrated with an experiment revealing the presence of certain ESR silent defects in oxygen-doped floating-zone ultrapure Si samples irradiated at room temperature with high-energy-high-fluence electron beams and pulse annealed up to 300 degrees C. New information is obtained by comparing the ESR spectra recorded at T = 120 K, without and with 1.06 mu m across-the-gap in situ illumination.

The synthesis of semiconductor nanocrystals with controlled doping is highly challenging, as often a significant part of the doping ions are found segregated at nanocrystals surface, even forming secondary phases, rather than incorporated in the core. We have investigated the dopant distribution dynamics under slight changes in the preparation procedure of nanocrystalline ZnO doped with manganese in low concentration by electron paramagnetic resonance spectroscopy, paying attention to the formation of transient secondary phases and their transformation into doped ZnO. The acidification of the starting solution in the co-precipitation synthesis from nitrate precursors lead to the decrease of the Mn2+ ions concentration in the core of the ZnO nanocrystals and their accumulation in minority phases, until similar to 79% of the Mn2+ ions were localized in a thin disordered shell of zinc hydroxynitrate (ZHN). A lower synthesis temperature resulted in polycrystalline Mn-doped ZHN. Under isochronal annealing up to 250 degrees C the bulk ZHN and the minority phases from the ZnO samples decomposed into ZnO. The Mn2+ ions distribution in the annealed nanocrystals was significantly altered, varying from a uniform volume distribution to a preferential localization in the outer layers of the nanocrystals. Our results provide a synthesis strategy for tailoring the dopant distribution in ZnO nanocrystals for applications ranging from surface based to ones involving core properties.

The results of the present Q-band electron spin resonance (ESR) investigation on amber colored cubic boron nitride (cBN) crystalline superabrasive powder (BORAZON CBN400) offer further support to the hypothesis that impurity ions with high natural abundant zero nuclear spin isotopes, distributed non-uniformly, are involved in the structure of the observed paramagnetic centers. One could thus explain the absence of any hyperfine structure in the multifrequency electron spin resonance spectra of both presently and previously investigated cBN crystalline powders and single crystals. The scanning electron microscopy, cathodoluminescence and photoluminescence studies performed on single crystallites selected from the same cBN400 batch further confirm the presence of electro- and photo-luminescent active impurity related centers, non-uniformly distributed in the cBN crystallite host lattice. The observation of an intense and reproducible thermoluminescence spectrum, up to high radiation doses, attributed to several trapping centers involving impurities, is also reported here.

The production and thermal stability of the irradiation paramagnetic point defects (IPPDs) in the as-grown, standard float-zone silicon (STFZ) and oxygen doped float-zone silicon (DOFZ) irradiated at room temperature with high fluence 3.5 MeV (1 x 10(17) cm(-2)) low energy and 27 MeV (2 x 10(16) cm(-2)) high energy electrons were investigated by Electron Spin Resonance (ESR). The nature and concentration of the IPPDs identified in the as-irradiated and isochronally annealed up to 300 degrees C samples by ESR measurements under intense above the gap 1.06 mu m in-situ laser illumination, were found to depend on oxygen concentration and electrons energy. While irradiation of STFZ with electrons produced as main IPPDs, besides divacancies, larger tetravacancy and pentavacancy cluster defects, irradiation of DOFZ resulted mainly in divacancies, vacancy-oxygen and interstitial oxygen-carbon impurity pairs. The observed variation in the nature of the main resulting IPPDs with the concentration of incorporated oxygen is explained by differences in the dominant defects production mechanisms. Thus in STFZ with lower oxygen concentration (1 x 10 16 cm(-3)) the dominant production mechanisms are the direct defects formation from a chain of neighboring vacancies by a cascade of secondary recoils across the path of the high energy irradiating particle and the divacancies diffusion and trapping/aggregation. Meanwhile, in DOFZ with larger oxygen content (1.2 x 10(17) cm(-3)) the primary vacancy and interstitial trapping by the oxygen and carbon impurities is the dominant defect production mechanism. Variations in the concentration and nature of the IPPDs observed during isochronal annealing are discussed in terms of defects thermal activated diffusion and recombination processes.

Enhancing the long term stable performance of silicon detectors used for monitoring the position and flux of the particle beams in high energy physics experiments requires a better knowledge of the nature, stability, and transformation properties of the radiation defects created over the operation time. We report the results of an electron spin resonance investigation in the nature, transformation, and long term stability of the irradiation paramagnetic point defects (IPPDs) produced by high fluence (2 x 10(16) cm(-2) ), high energy (27 MeV) electrons in n-type, P-doped standard floating zone silicon. We found out that both freshly irradiated and aged (i.e., stored after irradiation for 3.5 years at 250 K) samples mainly contain negatively charged tetravacancy and pentavacancy defects in the first case and tetravacancy defects in the second one. The fact that such small cluster vacancy defects have not been observed by irradiation with low energy (below 5 MeV) electrons, but were abundantly produced by irradiation with neutrons, strongly suggests the presence of the same mechanism of direct formation of small vacancy clusters by irradiation with neutrons and high energy, high fluence electrons, in agreement with theoretical predictions. Differences in the nature and annealing properties of the IPPDs observed between the 27 MeV electrons freshly irradiated, and irradiated and aged samples were attributed to the presence of a high concentration of divacancies in the freshly irradiated samples, defects which transform during storage at 250 K through diffusion and recombination processes. Published by AIP Publishing.

Although impurity doping of nanocrystals is essential in controlling their physical properties for various applications, the doping mechanism of ultrasmall, colloidal II-VI semiconductor nanocrystals, corresponding to the initial stages of growth, is not yet understood. In this study the concentrations of Mn2+ ions in the core, on the surface, and as an agglomerated separate phase in 2.9 nm cubic ZnS nanocrystals, prepared by a surfactant-assisted liquid liquid synthesis within 20 to 20 000 ppm nominal impurity concentration range, have been determined by quantitative multifrequency electron paramagnetic resonance. The unexpected strong decrease in the core doping efficiency with the nominal concentration increase, in contrast to the small variation of the doping efficiency for the surface-bound Mn2+ ions, and the sizable core doping efficiency observed for 1.8 nm nanocrystals were explained with the extended lattice defect assisted mechanism of incorporation. According to this mechanism, which is not size or shape limited, being active from the initial growth stages, the incorporation of Mn2+ ions takes place at surface sites with high binding energy on dislocation steps formed by the emerging stacking defects. High resolution transmission electron microscopy confirms the presence of such stacking defects in a large proportion of the investigated cubic ZnS nanocrystals, ensuring the operation of the proposed doping mechanism.