Sergiu Nistor

Amyloid beta (A(3) peptide aggregates are well-established biomarkers for Alzheimer's disease, though the complete etiology of this disorder remains elusive. Developing biointerfaces to elucidate the physiological roles of these peptides is essential. This study investigates the aggregation, fibrillation, and interaction of A(3 peptides with conductive, biocompatible nanostructured materials designed for applications involving neuronal cells. Various conductive, rigid, and flexible surfaces, both functionalized and non-functionalized with A(340 fibrils, were fabricated. These included glass substrates and poly(methyl methacrylate) electrospun fiber networks coated with gold via magnetron sputtering. The substrates were also functionalized through physical adsorption with poly-L-lysine and collagen, known to support cell proliferation, as well as with the inverse-A(340 peptide and an Amyloid Protein Non-A(3 Component, and the results were compared. The scaffolds were characterized using scanning electron microscopy, X-ray diffraction, atomic force microscopy, contact angle and electrical measurements, while their biological interactions were assessed using MTS assays, fluorescence imaging, and scanning electron microscopy. Fibroblast L929 and neuroblastoma SH-SY5Y cell lines were used as models, with results indicating an elevated cell viability, comparable to the control. The developed nanostructured surfaces are highly promising for integration into advanced neuromorphic engineering devices, as they have proven capable of maintaining their structural integrity when exposed to proteases.

The morphology, structure, composition, and con-duction electron properties of quasi-spherical tin nanocrystals (NCs) of 2.5 nm average diameter, with unstrained, bulk-like alpha-Sn diamond cubic structure, observed in dark cubic boron nitride (cBN) crystallites, were determined by correlated analytical high-resolution scanning transmission electron microscopy and multifrequency electron spin resonance (ESR) investigations. The narrow Lorentzian ESR line with g = 2.0028 is attributed to the conduction ESR of the alpha- Sn NCs, consistent with the temperature-and frequency-independent small g-shift and intensity reduction under high temperature (950 degrees C) vacuum annealing when the alpha-Sn NCs are thermally dissolved in the host cBN crystallites. The ESR linewidth and line intensity vs temperature dependences recorded in the 20 to 295 K range are quantitatively described considering the presence of discrete, quantum confinement-induced conduction electron energy levels with Delta QC/kB = 125 K separation, close to the theoretical value for conductive alpha-Sn NCs of 2.5 nm in diameter. The observed properties are tentatively explained with the predicted nanosize induced band-gap opening and change of band ordering from bulk alpha-Sn to small unstrained alpha-Sn NCs, resulting in a topological phase transition that also explains the predominantly s-like character of the conduction band electron orbitals.

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.

Previous electron spin resonance investigations correlated with data from cathodoluminscence and photoluminescence measurements have shown that impurity ions consisting mainly of isotopes with zero nuclear moments are involved in the structure of the observed paramagnetic point defects. In the present microstructural and compositional investigation we demonstrate that oxygen, carbon and silicon impurity atoms exhibiting low natural content of isotopes with non-zero nuclear spin are indeed present in cBN crystallites selected from amber coloured BORAZON CBN400 and CBN 500 super abrasive powders, as well as in the black coloured BORAZON CBN1000 and CBN Type 1. It is also shown that aggregates of impurity atoms are present next to the extended cBN lattice defects, which could explain the non-uniform distribution of the electro- and opto-active impurities reported in a spectroscopy investigation.

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.

The localization and distribution of the Mn2+ ions in two sol-gel deposited ZnO films doped with different manganese concentrations were investigated by electron paramagnetic resonance spectroscopy and analytical transmission electron microscopy. In the lightly doped sample the Mn2+ ions are mainly localized substitutionally at isolated tetrahedrally coordinated Zn2+ sites in both crystalline ZnO nanograins (34%) and surrounding disordered ZnO (52%). In the highly doped ZnO film, a much smaller proportion of manganese substitutes Zn2+ in the crystalline and disordered ZnO (10%). The main amount (85%) of manganese aggregates in a secondary phase as an insular-like distribution between the ZnO nanograins. The remaining Mn2+ ions (14% and 5% at low and high doping levels, respectively) are localized at isolated, six-fold coordinated sites, very likely in the disordered intergrain region. Annealing at 600 degrees C induced changes in the Mn2+ ions distribution, reflecting the increase of the ZnO crystallization degree, better observed in the lightly doped sample. (C) 2016 Elsevier B.V. All rights reserved.

We have shown in previous investigations that the low temperature collective magnetism observed in mesoporous cubic ZnS:Mn nanocrystalline powders prepared by colloidal synthesis, with nominal doping concentrations above 0.2 at.%, is due to the formation of Mn2+ clusters with distributed antifer romagnetic coupling localized in an amorphous phase found between the cubic ZnS:Mn nanocrystals. Here we investigate the composition, origin and thermal annealing behavior of this amorphous phase in such a mesoporous ZnS:Mn sample doped with 5 at.% Mn nominal concentration. Correlated analytical transmission electron microscopy, multifrequency electron paramagnetic resonance and Fourier transform infrared spectroscopy data show that the amorphous nanomaterial consists of unreacted precursor hydrated zinc and manganese acetates trapped inside the pores and on the surface of the cubic ZnS nanocrystals. The decomposition of the acetates under isochronal annealing up to 270 degrees C, where the mesoporous structure is still preserved, lead to changes in the nature and strength of the magnetic inter actions between the aggregated Mn2+ ions. These results strongly suggest the possibility to modulate the magnetic properties of such transition metal ions doped II-VI mesoporous structures by varying the synthesis conditions and/or by post-synthesis thermochemical treatments. (C) 2017 Elsevier B.V. All rights reserved.

The source of collective magnetism in II-VI semiconductor quantum dots (QDs) doped with Mn2+ ions at high nominal impurity levels is still under debate. In the particular case of mesoporous, self-assembled cubic ZnS:Mn QDs, quantitative electron paramagnetic resonance (EPR) studies have shown that the Mn2+ ions incorporated in the core and on the surface of the QDs cannot be responsible for the observed collective magnetism because they remain in a diluted paramagnetic state up to the 50 000 ppm nominal concentration. Here we investigate the composition, localization, structure, and magnetic properties of the aggregates of Mn2+ ions incorporated in the mesoporous cZnS:Mn as a possible source of the observed collective magnetism. Samples of mesoporous cubic ZnS:Mn prepared by coprecipitation at several nominal impurity levels from 200 to 50 000 ppm are investigated by EPR, magnetometry, and analytical high resolution (scanning) transmission electron microscopy. The low temperature magnetic properties of the Mn2+ aggregates change from paramagnetic-like, for samples with nominal impurity levels up to 2000 ppm, to ones specific to larger clusters with distributed antiferromagnetic coupling at higher concentrations, behaving superparamagnetically above a certain temperature. There is also strong evidence that the Mn2+ aggregates responsible for the observed low temperature collective magnetism are incorporated as an amorphous phase of mainly Mn-Zn-O composition, localized in the interstices and pores of the mesoporous structure of the cubic ZnS:Mn QDs.

One of the simplest routes to prepare polycrystalline Zn(OH)(2) is by coprecipitation, with zinc nitrate as a cation source. However, the addition of even minute amounts of manganese nitrate to the precursors used to prepare pure Zn(OH)(2) results in Mn2+ doped nanostructured ZnO. The comparison with other Mn2+ doped metal hydroxides prepared by the same coprecipitation method, involving metal nitrates precursors, shows that this behavior is unique, pertaining only to Zn(OH)(2). A systematic study of the samples prepared without and with variable amounts of Mn2+ ions, in the 1 to 5000 ppm nominal concentrations range showed that the re-routing of the reaction takes place even for the lowest nominal dopant concentration of 1 ppm. According to X-ray diffraction, transmission electron microscopy and Fourier transform infrared spectroscopy investigations, both crystallite size and morphology of the resulting nanostructured ZnO samples varied with the Mn2+ nominal concentration. Moreover, quantitative electron paramagnetic resonance investigations showed that the incorporation rate of the Mn2+ ions at different sites in the nanostructured ZnO depended on the nominal Mn2+ concentration. The results are discussed in terms of the coordination properties of the Mn2+ and Zn2+ ions and the nature of the reaction precursors.

The distribution and interaction of isolated Mn2+ impurity ions incorporated in 2.9 nm average diameter cubic ZnS quantum dots (QDs), prepared by surfactant-assisted liquid-liquid synthesis with initial impurity concentrations in the 20-50,000 ppm range, has been investigated by electron paramagnetic resonance (EPR) spectroscopy. The well resolved spectra, observed in the whole investigated concentration range, reflect the localization of the Mn2+ ions in the core and on the surface of the cZnS: Mn QDs at isolated sites. According to the analysis of the dependences of the concentration of incorporated isolated Mn2+ ions vs. initial impurity concentration and of the core localized Mn2+ ions spectra line-width vs. actual concentration, the isolated Mn2+ ions remain in the whole concentrations range in a diluted paramagnetic state characterized by dipolar magnetic interactions. Pulse EPR measurements of the spinespin dipolar interaction for the incorporated Mn2+ ions confirm their diluted distribution, which excludes these ions as a possible source of collective magnetism properties. (C) 2015 Elsevier B.V. All rights reserved.

The sites of incorporation of Cu2+ impurity ions in Bi12GeO20 single crystals co-doped with copper and vanadium have been investigated by electron paramagnetic resonance (EPR). While the X-band EPR spectra consist of a simple broad (Delta B similar to 50 mT) line with anisotropic lineshape, the W-band EPR spectra exhibit well resolved, strongly anisotropic lines, due to transitions within the 3d(9)-D-2 ground manifold of the Cu2+ ions. The most intense group of lines, attributed to the dominant Cu2+(I) center, displays a characteristic four components hyperfine structure for magnetic field orientations close to a direction. The g and A tensor main axes are very close to one of the 12 possible sets of orthogonal , and crystal directions. Several less intense lines, with unresolved hyperfine structure and similar symmetry properties, mostly overlapped by the Cu2+(I) spectrum, were attributed to Cu-2 (+)(II) centers. The two paramagnetic centers are identified as substitutional Cu2+ ions at Bi3+ sites with low C-1 symmetry, very likely resulting from different configurations of neighboring charge compensating defects. (C) 2015 Elsevier Inc. All rights reserved.

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.

The analysis of the sequence of electron paramagnetic resonance (EPR) spectra of trace amounts of substitutional probing paramagnetic ions incorporated in (nano)crystalline samples submitted to isothermal and isochronal pulse annealing treatments can offer a wealth of information on the thermally induced compositional and structural changes of the host material. The potential of this new thermal analysis method is illustrated here with results of such investigations on the thermal decomposition of crystalline zinc hydroxide (Zn(OH)(2)) and anhydrous zinc carbonate basic (Zn-5(CO3)(2)(OH)(6)) precursors containing trace amounts of substitutional Mn2+ probing ions into nanostructured zinc oxide-ZnO. The quantitative analysis of the sequence of isochronal pulse annealing EPR spectra could provide, besides the thermal decomposition curves of the two precursors, additional information about the structure of the resulting nanostructured ZnO, some of it hard to get by standard structural diffraction techniques. The analysis of both isochronal and isothermal pulse annealing EPR data was further used to investigate the crystallization mechanism of the initially formed nanostructured disordered ZnO and to quantitatively describe the further growth of the resulting ZnO nanocrystals with the increasing annealing temperature and duration.

Electron paramagnetic resonance (EPR) spectroscopy has been extensively employed to investigate the presence, localization, distribution and interaction with the host crystalline lattice of the paramagnetic point defects (intrinsic defects and transition metal ions) in semiconductors. The retrieval of such information for nanostructured semiconductors is considerably more difficult, due to the high disorder level in such systems, reflected in broad, featureless EPR spectra. We show here how, with proper adjustments of the EPR experiments and accurate numerical analysis of the resulting spectra, it was possible to obtain more accurate information regarding the localization and structure of various Mn2+ centers in ZnS and ZnO semiconductor nanoparticles (NPs). This lead to the observation and investigation of size related effects such as the presence of the extended lattice defect assisted incorporation of impurities in small (similar to 3 nm) cubic ZnS NPs, the dominant size induced lattice disorder observed for ZnO NPs, independent of the synthesis procedures, or the three steps decomposition of the epsilon-Zn(OH)(2) disordered shell of ZnS NPs with formation of new oxy-hydrated zinc compounds. These effects can be used to synthesize semiconductor nanoparticles with controlled size distribution, doping level and functionalized surfaces for specific technological applications.

Trace amounts of substitutional Mn2+ ions and shallow donors magnetic centers were identified by electron paramagnetic resonance (EPR) in crystalline Zn(OH)(2) prepared by precipitation of a Zn-nitrate solution with NaOH. Strong changes in the Mn2+ ions spectrum, as well as a sharp increase in the concentration of the shallow donor centers were observed by EPR in the 110-140 degrees C temperature range, during pulse annealing experiments in air up to 240 degrees C. They reflect the decomposition of the crystalline Zn(OH)(2) host lattice into nanocrystalline ZnO, confirmed by X-ray diffraction and thermal analysis measurements. Accurate spin Hamiltonian parameters of the observed paramagnetic centers were determined by lineshape simulation and fitting of the EPR spectra, to be used as reference data in further studies of nanocrystalline systems involving Zn(OH)(2). (C) 2012 Elsevier B.V. All rights reserved.

The thermal stability above 300 K of the hole-trapped Fe3+ centers, formed by X-ray irradiation at 80 K in chlorinated SrCl2:Fe2+ crystals, has been investigated by Electron Paramagnetic Resonance. In the temperature range of 300 - 520 K, the trigonal Fe3+ center completely transforms into the cubic Fe3+ center, which further decays up to 700 K. The formation and transformation of the trigonal Fe3+ center, containing off-center Fe3+ ions, is associated with the presence and thermally activated movement of the interstitial Cl- ions, present in excess in chlorinated SrCl2:Fe2+ crystals.

The fast decomposition of hydrozincite [Zn-5(CO3)(2)(OH)(6)] into ZnO observed in the transmission electron microscope could be slowed down and investigated in situ by operating the microscope at very low electron beam current densities and cooling the specimen down to -160 degrees C. Thus, it was possible to observe and pursue the distinct structural steps of the disruption of the hydrozincite lattice due to the energetic emission of H2O and CO2 gases. The initially formed disordered ZnO phase was found to further crystalize resulting in a mesoporous structure of small ZnO nanocrystals.

Nanocrystals (NCs) of II-VI semiconductors of few nanometers average size, called quantum dots (QDs), are now intensely investigated as radiation detectors. Besides the expected quantum confinement and influence of surface states, our electron paramagnetic resonance investigations of cZnS QDs doped with Mn2+ ions, correlated with structural data, underline that other properties should be also taken into consideration in developing the II VI semiconductor QDs as radiation detectors. Thus, the preferential localization of Mn2+ in the core of the cubic ZnS QDs at substitutional Zn2+ cation sites next to a stacking lattice defect is expected to lead, besides changes in the impurity energy levels, to specific aggregation properties. An outer shell of different composition can also influence the structural properties of the QDs core with effects on the optical properties as well. (C) 2013 Elsevier Ltd. All rights reserved.

Thermally induced changes in the structure and composition of the shell of tightly aggregated cubic ZnS/Zn(OH)(2) core shell quantum dots of 1.9 nm average core size were investigated by multifrequency electron paramagnetic resonance of Mn2+ probing ions. The observed three-steps temperature induced transformation of the Mn2+ surface centers in the 80-450 degrees C temperature range Zn(OH)(2) shell into ZnO, with the formation of the Zn2O(OH)(2) and Zn4O3(OH)(2) intermediate nanocompounds. The presence of a 0.3 to 1.9 nm thick surface layer of disordered nanomaterial separating the cubic ZnS cores and its shrinking to a few atomic layers by mass loss after annealing up to 350 degrees C was observed by high resolution transmission electron microscopy. Unlike the single step dehydration around 120 degrees C of the bulk epsilon-Zn(OH)(2), the complex decomposition of the epsilon-Zn(OH)(2) shell is attributed to its nanosized, disordered structure.

The presence and structure of paramagnetic point defects in C-13 and O-17 implanted ultrapure Si single-crystal material, two impurities which seem to play a major role in the detectors performance degradation and radiation resistance enhancement, respectively, are reported before and after irradiation with 6 MeV electrons. The investigation, performed by Q-band electron spin resonance spectroscopy in the 300 - 10 K temperature range, included also reference ultrapure and O-16 doped single-crystal Si-platelets. It resulted in the observation of points defects associated with lattice defects as dangling bonds and impurities.

The correlation of the lattice disorder with the nanocrystal average size, in ZnO nanocrystals synthesized by several different methods, has been quantitatively monitored by line shape analysis of the multifrequency electron paramagnetic resonance (EPR) spectra of low concentrations of substitutional Mn2+ probing ions. The observed correlation between the line broadening parameter of the spectrum and the average ZnO nanocrystals size, independent of the synthesis procedure of the ZnO nanocrystals, demonstrates the dominance of the size related strain/disorder. On the basis of this result, a new method for determining the average ZnO nanocrystal size from the quantitative analysis of the EPR spectra of the Mn2+ probes was derived. The nanocrystallization of the disordered ZnO formed by the thermal decomposition of hydrozincite was monitored using this procedure. The observed ZnO nanocrystallite growth kinetics at lower temperatures was described by a structural relaxation mechanism consisting of the local ordering by rearrangements of the atoms in the interfaces/grain boundaries, with a growth activation energy of similar to 23 kJ/mol. When the nanostructured ZnO was more than 75% crystallized, another growth mechanism of the nanocrystals was found to occur, driven by the reduction of the total grain boundary energy.

Accurate determination of the spin Hamiltonian (SH) parameters, describing the electron paramagnetic resonance (EPR) spectra of paramagnetic impurity ions in wide band gap semiconductor nanocrystals, is essential for determining their localization and quantum properties. Here we present a procedure, based on publicly available software, for determining with higher accuracy the SH parameters of isolated Mn2+ impurity ions in small cubic ZnS nanocrystals. The procedure, which can be applied to other cubic II-VI semiconductor nanocrystals as well, is based on the analysis of both low and high frequency EPR spectra with line shape simulation and fitting computing programs, which include the hyperfine forbidden transitions and line broadening effects. The difficulties, limitations and errors which can affect the accuracy in determining some of the SH parameters are also discussed. (C) 2011 Elsevier Inc. All rights reserved.

The EPR, radioluminescence, and photoluminescence of cubic ZnS (cZnS) nanocrystals (NCs) with a narrow size distribution centered at 2 nm, doped with 0.1, 0.2, and 0.5 at.% Mn2+ ions were investigated. Besides the main lines from substitutional Mn2+ ions localized in the core of the NCs next to a stacking defect, the EPR spectra exhibited two broader hyperfine sextets, attributed to the so-called Mn(II)and Mn(III) surface centers, which could be separated by adequate thermal treatments. The contribution to the photoluminescence from the Mn2+ ions at various sites was further determined from the analysis of the steady-state and time-resolved photoluminescence data from cZnS: Mn NCs subjected to thermal treatments and from cZnS: Mn single crystals. Thus, the main emission consisting of two intense overlapping bands peaking at 596 and 630 nm was attributed to the T-4(1)-(6)A(1) transition of the substitutional Mn2+ ions in the core of the cZnS nanocrystals and to residual aggregated Mn2+ ions, respectively, the last ones being responsible for a broad EPR line observed in the X-band spectrum. The Mn(II) and Mn(III) centers, consisting of Mn2+ ions in the oxidized and hydrolyzed surface layer of the NCs, respectively, are only indirectly involved in the energy transfer to the substitutional Mn2+ centers, very likely through pairs interaction.

The structural changes of cubic ZnS (cZnS) nanocrystals (NCs) doped with 0.2 at.% Mn2+ pulse annealed in vacuum and in air, up to 500 A degrees C, were investigated by multifrequency electron paramagnetic resonance (EPR), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The samples, prepared by a surfactant (Tween20)-assisted liquid-liquid reaction at pH = 6, consist of NCs with a tight size distribution around 3 nm and high crystallinity self-assembled into a stable mesoporous structure. The EPR spectra of the as prepared samples contain only the characteristic lines of the substitutional Mn2+(I) centers. No spectra from Mn2+ ions localized in (hydro)oxidized regions of the NCs surface were observed. The absence of such a surface layer could explain the stability of the cubic (sphalerite) structure observed by XRD and TEM in the investigated cZnS:Mn NCs annealed in vacuum up to 500 A degrees C. The observation of the cubic-hexagonal transformation for the same NCs annealed in air supports the role of such layer in promoting this structural transformation. The narrowing of the EPR spectral lines above 200 A degrees C with the increase in the average size of the cZnS:Mn crystallites was observed. The effect was more pronounced for the sample annealed in air. EPR also revealed the formation of minute amounts of substitutional Mn2+-type centers in a hexagonal ZnO structure at T similar to 300 A degrees C, corresponding to the early stages of the thermally induced oxidation of the cZnS:Mn NCs.

The formation and crystallization of disordered nanosized ZnO resulting from the thermal decomposition of nanocrystalline hydrozincite [Zn-5(CO3)(2)(OH)(6)] has been Observed and investigated during pulse annealing experiments Up to 625 degrees C in air or vacuum by electron paramagnetic resonance of trace amounts of substitutional Mn2+ impurity ions, in correlation with X-ray diffraction and transmission electron microscopy measurements. The mesoporous structure of the disordered ZnO, which initially forms in air and vacuum at 225 and 175 degrees C, respectively, further transforms into nanocrystalline ZnO of increasing particle size and improved lattice quality at higher annealing temperatures. The crystallization process, which does not affect the concentration of the substitutional impurity ions, as well as the simultaneous presence of both disordered and crystalline phases, should be considered in further applications of the resulting nanosized ZnO.

A mesoporous structure of self-assembled nanocrystals of cubic ZnS doped with Mn2+ ions with a homogeneous distribution of pores of similar size was synthesized at room temperature by a surfactant-assisted liquid-liquid reaction. The component nanocrystals exhibit a high crystallinity and a tight size distribution centered at 2 nm, as well as the narrowest Electron Paramagnetic Resonance (EPA) spectra linewidth and the best resolution reported so-far, effects attributed to self-assembling. The observed EPA spectra consist of lines from the substitutional Mn2+(I) and surface Mn2+(II) and Mn2+(III) centers. Here we show that, in contrast with previous reports, our EPA spectra are highly sensitive to structural changes during pulse annealing in vacuum up to 500 degrees C. The changes are related to the transformation of the surface Mn2+ centers in new Mn2+ centers, attributed to an oxidation process in which the thermal decomposition of the Tween 20 additive, also observed by EPA, seems to be involved. We have also been able to observe, for the first time by EPR spectroscopy, the formation of the ZnO phase and the nanocrystals size increase, which occur during annealing up to 500 degrees C, structural changes confirmed by XRD and TEM observations on the samples previously investigated by EPR.

A multifrequency Electron Paramagnetic Resonance (EPR) investigation of Ce3+ impurities in PbWO4 single-crystals at the conventional microwave frequency (CMF) (X-band: 9.43 GHz) and at the high frequencies/fields (HF) 95, 190 and 285 GHz was carried out. The resulting spectra are well described at all frequencies by an axial spin-Hamiltonian corresponding to an effective spin one-half system in a tetragonal site symmetry. The diagonal values of the effective g matrix of the lowest doublet of the ground multiplet, g(parallel to) and g_, are frequency dependent at high fields. For the magnetic field perpendicular to the tetragonal axis, the g_-parameter exhibits also a small azimuthal angular dependence, which is frequency dependent, corresponding to the tetragonal S-4 symmetry. These HF effects are associated with the mixing by the large Zeeman interaction of some of the upper-lying doublets of the ground multiplet into the lowest-lying doublet states. The CMF and multifrequency HF-EPR analysis gives a good description of the magnetic properties and allows an estimation of the crystal field splitting of the ground multiplet of Ce3+ ions with tetragonal symmetry S-4 in the PbWO4 scintillator. (c) 2009 Elsevier BM. All rights reserved.

Nanocrystals of cubic ZnS (cZnS) doped with 02 % mol Mn2+, self-assembled into a mesoporous structure, have been prepared at room temperature by a surfactant-assisted liquid-liquid reaction The X-ray diffraction measurements confirm the formation of a sponge-like mesoporous structure built from ZnS nanocrystals with cubic (sphalerite) structure and pores of similar diameter of (1 8 +/- 0 2) nm. The Transmission Electron Microscopy (TEM) images show that the mesoporous structure consists of nanocrystals of cZnS with a tight size distribution centered around the average diameter value (21 +/- 0 3) nm The analysis of the observed Election Paramagnetic Resonance (EPR) spectrum demonstrates the presence of the Mn2+ activating ions at isolated sites in the mesoporous material, resulting in three types of paramagnetic centers called Mn2+(I), Mn2+(II) and Mn2+(III) The EPR spectrum of the Mn2+(I) center, attributed to substitutional Mn2+ ions at Zn2+ cation sites in the ZnS nanocrystals, exhibits the smallest linewidth values reported so far, reflecting an increased lattice ordering The high quality of the nanocrystals forming the mesoporous cZnS Mn, as reflected in a tight nanocrystallites size distribution and reduced crystallites lattice disorder, is attributed to the restraining effect of the self-assembling

Low-frequency (X-band) electron spin resonance (ESR) investigations on commercially available large-grained cubic boron nitride (cBN) superabrasive powders of various coloration, combined with high-frequency (W-band) ESR measurements on oriented submillimeter-size single crystallites selected from the same powder samples, resulted in a clear identification of several types of paramagnetic point defects. The resulting spin Hamiltonian parameters describing the ESR spectra observed in the 3-293 K temperature range and the photosensitivity of the paramagnetic defects observed in amber-colored cBN samples are reported. It is shown that the nature of the paramagnetic centers depends on the color of the investigated samples and that, in many cases, uncontrolled impurities seem to be involved in their structure.

Electron paramagnetic resonance spectra from substitutional Mn2+ ions in quantum dots of cubic ZnS with tight size distribution centred at 2 nm were recorded in the 9.8 GHz and 34 GHz frequency bands. Their quantitative analysis with line shape simulation and fitting computer programs accounting for both forbidden transitions and line broadening effects demonstrate the presence of a local axial distortion attributed to a neighbouring extended planar stacking defect. The presence of such extended lattice defects, confirmed from a high resolution transmission electron microscopy study on presently investigated cubic ZnS quantum dots, seems to be essential in the incorporation and localization of Mn2+ activating ions in other cubic II-VI semiconductor quantum dots as well.

Multifrequency electron paramagnetic resonance (EPR) and high resolution transmission electron microscopy (HRTEM) investigations were performed on small (2 nm) cubic ZnS nanocrystals (quantum dots-QDs) doped with 0.2% mol Mn2+, self-assembled into a mesoporous structure. The EPR data analysis shows that the substitutional Mn2+ ions are localized at Zn2+ sites subjected to a local axial lattice distortion, resulting in the observed zero-field-splitting parameter vertical bar D vertical bar = 41 x 10(-4) cm(-1). The local distortion is attributed to the presence in the second shell of ligands of a stacking fault or twin, which alters the normal stacking sequence of the cubic structure. The HRTEM results confirm the presence of such extended planar defects in a large percentage of the investigated QDs, which makes possible the proposed substitutional Mn2+ impurity ions localization model. Based on these results it is suggested that the high doping levels of Mn2+ ions observed in cubic ZnS and possible in other II-VI semiconductor QDs prepared at low temperatures can be explained by the assistance of the extended lattice defects in the impurities incorporation.

Nanocrystalline cubic ZnS doped with 0.2% mol manganese, exhibiting a stable mesoporous structure, was synthesized at room temperature by a non toxic surfactant-assisted liquid liquid reaction. The X-ray diffraction measurements demonstrate the formation of a sponge-like mesoporous material built from cubic ZnS nanocrystals of 1.8 nm average sizes, with a tight distribution of pores of 1.8 nm mean diameter. The transmission electron microscopy images confirm the formation of the mesoporous structure with walls of 3.1 nm mean thickness built from cubic ZnS nanocrystallites of 2.1 nm average size. The resulting tight distribution of crystallites and pores yields a well resolved Electron Paramagnetic Resonance spectrum, with the narrowest reported component lines attributed to three types of isolated Mn2+ centers, called Mn2+ (I), Mn2+ (II) and Mn2+ (III). From the analysis of the spin Hamiltonian parameters it is shown that in the Mn2+ (I) centers the paramagnetic ion is situated at substitutional Zn sites in the ZnS nanocrystals, being also subjected to a small axial distortion. The relative concentration changes under thermal treatment experiments strongly suggest that in both Mn2+ (II) and Mn2+ (III) centers the Mn2+ ion is localized on the surface of the ZnS nanocrystallites, being bond to an oxygen ion in the first case and to an additional water molecule in the second case.

We report the synthesis, by a surfactant-assisted liquid-liquid reaction, of nanocrystalline ZnS doped with 0.2 mol% Mn2+ ions self-assembled in a mesoporous structure. The XRD measurements demonstrate the formation of a sponge-like mesoporous material with a tight distribution of pores of 1.8 nm mean diameter built from cubic ZnS nanocrystals of 1.8 nm average size. TEM investigation confirms the formation of the mesoporous structure with walls of 3.1 nm mean thickness built from nanocrystallites of cubic ZnS. The ordering effect of self-assembling, which is reflected in the tight size distribution of crystallites and pores, might be also responsible for the well resolved EPR spectra, attributed to the presence of three types of isolated Mn2+ paramagnetic centers. (C) 2008 Elsevier Ltd. All rights reserved.

The X (9.8 GHz)-band electron paramagnetic resonance (EPR) properties of substitutional Mn2+ ions in high quality cubic ZnS single crystals grown from PbCl2 flux have been thoroughly investigated. Accurate spin Hamiltonian (SH) parameters: g = 2.002 25 +/- 0.000 06; a = (7.987 +/- 0.008) x 10(-4) cm(-1) and A = -(63.88 +/- 0.02) x 10(-4) cm(-1) were obtained by simulation and fitting to the experimentally allowed transitions recorded for the magnetic field aligned within +/- 0.25 degrees along the main crystal axes. The normally forbidden hyperfine M = + 1/2 -1/2, Delta m = +/- 1 transitions were also observed. Their position was found to be in agreement, within the experimental accuracy of Delta H = +/- 0.01 mT, with calculations using the same SH parameters. The angular variation of the ratios of the intensities of the central forbidden to the allowed transitions could be accounted for only by including an additional constant contribution. The observed line broadening of the M = +/- 1/2 +/- 3/2 and +/- 3/2 +/- 5/2 fine structure transitions and their line width variation in a (110) plane have been quantitatively described by considering a random distribution of lattice strains at the Mn2+ impurity ions. The influence of the forbidden transitions and line broadening on the EPR spectra line shape of the Mn2+ ions in cubic ZnS crystalline powders is also examined.

A multifrequency electron paramagnetic resonance (EPR) investigation of Nd3+ impurities in PbWO4 single-crystals at the conventional microwave frequency (MF) 9.43 GHz, and at the 95, 190, and 285 GHz high frequencies was carried out. The resulting spectra are well described at all frequencies by an axial spin-Hamiltonian corresponding to an effective electron spin of one-half and to a tetragonal symmetry. For the magnetic field along the tetragonal axis, the g(-)factor and the hyperfine constant A of the lowest doublet of the ground multiplet decreases with frequency increase. For the magnetic field perpendicular to the tetragonal axis, the g(perpendicular to)-factor exhibits a small azimuthal angular dependence that increases with increasing the frequency due to the S-4 site symmetry. The azimuthal angular dependence allows to clearly distinguish between different local axial symmetries. These properties are interpreted as high field/frequency (HF) effects associated with the mixing by the large Zeeman interaction of some of the upper-lying doublets of the ground multiplet into the lowest-lying doublet states. We show that from the combined analysis of the multifrequency MF- and HF-EPR spectra and of the optical data, an accurate description of the ground multiplet of the Kramers rare earth ions in solid matrices can be derived.

Several hole trapped centres, namely Tl2+, self-trapped hole and A-type centres, were observed by ESR in PbBr2:Tl single crystals after X-ray irradiation at 77 K. The corresponding spectra are visible up to 200 K for all three defect centres. The STH centres are observed at higher temperatures than in the undoped PbBr2 single crystals, probably due to the stabilising effect of the Tl+ impurities. The ESR parameters of the Tl2+ centre point to stronger covalency effects in PbBr2 than in the isostructural PbCl2 crystals. All hole trapped centres started decaying around 160 K, probably due to recombination with nonparamagnetic electron trapped centres. Besides a small concentration of self-trapped electron centres, no other electron trapped centres were observed. (c) 2008 Elsevier B.V. All rights reserved.

Single crystallites of superhard, semiconducting, n-type, amber colored and p-type, blue colored, Be-doped cubic boron nitride have been irradiated either with UV (350 nm) light or with an intense beam of accelerated (1 MeV) electrons. The examination of the irradiated samples at low temperatures by high frequency W (95 GHz)-band electron spin resonance reveals several new, radiation-induced, isotropic paramagnetic centers. The UV irradiation of both types of crystals yields centers involving very likely protons. In the amber c-BN crystals the irradiation with I MeV electrons results in the formation of vacancy associated paramagnetic defects and quasi-free electrons in colloidal particles. (C) 2008 Elsevier B.V. All rights reserved.

Pure, nanocrystalline cubic ZnS forming a stable mesoporous structure was synthesized at room temperature by a non-toxic surfactant-assisted liquid-liquid reaction, in the 9.5-10.5 pH range of values. The appearance of an X-ray diffraction (XRD) peak in the region of very small angles (similar to 2 degrees) reveals the presence of a porous material with a narrow pore size distribution, but with an irregular arrangement of the pores, a so-called worm hole or sponge-like material. The analysis of the wide angle XRD diffractograms shows the building blocks to be ZnS nanocrystals with cubic structure and average diameter of 2 nm. Transmission electron microscopy (TEM) investigations confirm the XRD results; ZnS crystallites of 2.5 nm with cubic (blende) structure are the building blocks of the pore walls with pore sizes from 1.9 to 2.5 nm, and a broader size distribution for samples with smaller pores. Textural measurements (N-2 adsorption-desorption isotherms) confirm the presence of mesoporous ZnS with a narrow range of small pore sizes. The relatively lower surface area of around 100 m(2)/g is attributed to some remaining organic molecules, which are filling the smallest pores. Their presence, confirmed by IR spectroscopy, seems to be responsible for the high stability of the resulting mesoporous ZnS as well.

The formation of the electron trapped Fe+(IV) centre, produced by X-ray irradiation at 80 K and further annealing at temperatures of up to 700 K in chlorinated SrCl2: Fe crystals, has been investigated by Electron Paramagnetic Resonance. Our studies report the transformation of the monoclinic Fe+(III) centre into the axial Fe+(IV) centre above 450 K. The formation of the Fe+(IV) centre is attributed to the presence and thermally activated movement of neighbouring interstitial chlorine and alkali impurity Ne ions. (c) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The properties of the electron paramagnetic resonance spectra of Gd3+ ions in PbWO4 single crystals have been investigated in the X-band microwave frequency region, in the 1.5 to 290 K temperature range. The observed S-4 symmetry of the local crystal field at the Gd3+ impurity ions strongly suggests that the Gd3+ ions substitute for the Pb2+ lattice cations, with charge compensation at a distance. The spin Hamiltonian parameters are comparable with those of the Gd3+ ions in other isomorphous tungstates. The temperature variation of the fine structure parameters B-2(0) and B-4(0) points to an energy transfer between the impurity ions and the host lattice, which takes place mainly through a local vibrational mode of frequency omega = 3.1 x 1013 rad s(-1).

A full vibronic spectrum has been measured for the first time by LNT Cathodoluminescence in HPHT c-BN amber-coloured microcrystalline samples. The related BN1 centre at 3.293 eV seems not created by electron irradiation in this case and the accurately determined phonon energy (141 +/- 3 meV) could be related to LO phonon at X point in Brillouin Zone (BZ) of c-BN, as determined by CL results obtained at indirect gap. Consequently, BN1 centre has not the full cubic symmetry of c-BN, as being due to N interstitials. The interpretation of the results is possibly twofold: either we are observing a vibronic spectrum with ZPL at BN1 centre, together with other two centres called PF-1 and PF-2 at 3.573 and at 3.412 eV, respectively, or, since all the 6 or 7 observed peaks are exactly equally spaced, the whole vibronic spectrum is related to a ZPL line at 3.573 eV. This new interpretation seems to be in better agreement with the general theory of colour centres. (c) 2005 Elsevier B.V. All rights reserved.

Electron-trapped Fe+-type centers, produced by x-ray irradiation at 80 K and further annealing at higher temperatures in iron-doped SrCl2 single crystals grown in chlorine gas, have been investigated by electron paramagnetic resonance. The Fe+(III) and Fe+(IIIa) centers, produced by annealing at temperatures higher than 200 K, exhibit monoclinic local symmetry with the two g down arrow- tensor principal axes situated in the (110) plane slightly tilted away from the [001] and [1-10] directions, respectively. The Fe+(IV) center, observed after several cycles of irradiation and annealing to 700 K, exhibits tetragonal local symmetry around and a well-resolved four-component structure, attributed to the superhyperfine interaction with a neighboring monovalent impurity ion. The presence and properties of the low symmetry radiation-induced Fe+ paramagnetic centers are attributed to trapping and the thermally activated movement of chlorine interstitials. Both precursor Fe2+ and resulting Fe+ centers are perturbed by these interstitials, which are introduced in SrCl2:Fe crystals during growth under a chlorine atmosphere.

Two samples of large-grained commercial superabrasive cubic boron nitride crystalline powders in different shades of amber coloration have been investigated by low frequency X (9.4 GHz)-band electron paramagnetic resonance (EPR) spectroscopy at room and low (T < 15 K) temperatures. Both samples contain three spectra component lines, A1, A2 and A3, in the same proportion, and the total concentration of the corresponding paramagnetic centers being proportional to the intensity of the amber coloration. After in situ broad-band UV illumination at low temperature, the intensity of the A1 component line becomes dominant. The observed effects are attributed to electron trapping at EPR silent A1(+) precursor centers, which seem to coexist with the A1 centers and to the eventual ionization of the paramagnetic A3 centers responsible for the A3 component line.

The temperature variation of the fine and hyperfine parameters of Mn2+ in single crystals of PbWO4 in the low temperature range reveals the presence of a resonant mode of frequency omega = 8.8 x 10(12) rad s(-1). Moreover, above 60 K, where the temperature induced broadening becomes dominant, a T-2 variation of the relaxation time was inferred from the analysis of the temperature dependence of the Mn2+ linewidth. This variation is attributed to a Raman relaxation process due to the coupling with the same local resonant mode.

Cubic boron nitride (c-BN) is a synthetic material which exhibits exceptional physicochemical properties such as: hardness, thermal conductivity, thermo-chemical stability, semiconducting properties and radiations resistance. Such outstanding properties make it a promising multifunctional material for applications in extreme conditions, as those found in the outer space environment. Its further use for such applications requires, however, a much better understanding of the lattice defects and radiation damage properties. Here we present the results of multifrequency ESR studies concerning the native and radiation induced point defects in crystalline c-BN under irradiation with high intensity 1MeV electron beams.

High frequency (95 GHz) ESR measurements have been performed down to 5 K, on three cubic boron nitride (c-BN) single crystals doped with beryllium. The measured samples exhibit at low temperature different ESR spectra, which are sensitive to low temperature in situ illumination using a series of Kr+- and Ar+-laser lines. The analysis of the ESR spectra resulted in the identification of several native paramagnetic centers responsible for the observed component spectra lines. (C) 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The electron paramagnetic resonance (EPR) properties of the Mn2+ ions in PbWO4 single crystals grown by the Czochralski method have been investigated in the X-band microwave frequency, at T = 20 K. The angular dependence of the EPR line positions obtained by rotating the magnetic field in the main crystallographic planes shows that the local symmetry at the Mn2+ impurity ions is tetragonal, strongly suggesting that the Mn2+ ions substitute for the Pb2+ lattice cations, without charge compensation. The resulting spin Hamiltonian parameters compare well with the corresponding values for the Mn2+ ions in other isomorphous tungstates. The observed strong angular variation of the EPR linewidth has been quantitatively described considering a random distribution of lattice strains. (C) 2003 Elsevier Ltd. All rights reserved.

Thallium related paramagnetic centers of Tl2+ (6s(1)) and Tl-0 (6p(1)) type were produced by low temperature x-ray irradiation in ferroelectric Rb2ZnCl4:Tl single crystals. Extensive EPR investigations have been performed in order to elucidate their intrinsic properties and sensitivity as paramagnetic probes for structural phase transitions studies. Compared to the s-type Tl2+ centers, already used in many such studies, it was found that the p-type Tl-0 centers are much more sensitive to the small variations in the local crystal field associated with these transformations. Their EPR spectra provided information about the unit cell tripling in the P2(1)cn phase, as well as the symmetry lowering and lattice dynamics in the C1c1 phase. The temperature induced, continuous changes observed in the EPR spectra of both Tl-0 and Tl2+ centers were explained by the influence of the soft modes responsible for the 74-K structural phase transition.

Hydroxyapatite (HA) thin films has been successfully deposited by Nd:YAG laser ablation lambda = 532 nm. The morphology and microstructure of the deposited layers was studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution electron microscopy (HREM). Polycrystalline HA films were directly obtained with the substrate at 300 degreesC and without introducing water vapors in the deposition chamber. Electron paramagnetic resonance (EPR) measurements show that the oxygen stoichiometry in the HA films is also maintained. Depositions performed at lambda = 335 nm laser wavelength and 300 degreesC substrate temperature resulted in polycrystalline layers of mixed composition of HA and tricalciumphosphate (TCP). (C) 2004 Elsevier Ltd. All rights reserved.

Cubic boron nitride (c-BN) crystalline superabrasive powder (Borazon** CBN 400), consisting of 200-300 microns sized amber colored crystallites prepared by HP/HT synthesis, has been examined from 2.1 K to 293 K by X-band ESR spectroscopy. The observed spectrum consists of a component line A1, visible in the whole temperature range, and two component lines A2 and A3, visible at high and low temperatures, respectively. The A1 and A3 lines originate from transitions inside S = 1/2 ground states of distinct paramagnetic species and A2 from transitions inside an excited state of another paramagnetic center. The intensity of the A1 and A3 lines changes differently during in situ low temperature illumination in the UV-VIS range. (C) 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The axially symmetric Fe+(II) center observed in SrCl2:Fe2+ crystals has been studied by the electron nuclear double resonance (ENDOR) technique in the microwave X and Q bands. This center is produced only in crystals grown in chlorine atmosphere and x-ray irradiated at low temperature (below 100 K). The analysis of the ENDOR spectra unambiguously confirms the structural model earlier suggested by the electron paramagnetic resonance (EPR) study, as a Fe+ ion strongly displaced off center along an axis, almost in the center of the square determined by the four nearest Cl- ligands. The unpaired spin densities f(3s) and f(3p) in the 3s and 3p chlorine orbitals have been determined from the resulting ENDOR parameters.

Neuroglobin is a recently discovered member of the globin superfamily. Combined electron paramagnetic resonance and optical measurements show that, in Escherichia coli cell cultures with low O-2 concentration overexpressing wild-type mouse recombinant neuroglobin, the heme protein is mainly in a hexacoordinated deoxy ferrous form (F8His-Fe2+-E7His), whereby for a small fraction of the protein the endogenous protein ligand is replaced by NO. Analogous studies for mutated neuroglobin (mutation of E7-His to Leu, Val, or Gin) reveal the predominant presence of the nitrosyl ferrous form. After sonication of the cells wild-type neuroglobin oxidizes rapidly to the hexacoordinated ferric form, whereas NO ligation initially protects the mutants from oxidation. Flash photolysis studies of wild-type neuroglobin and its E7 mutants show high recombination rates (k(on)) and low dissociation rates (k(off)) for NO, indicating a high intrinsic affinity for this ligand similar to that of other hemoglobins. Since the rate-limiting step in ligand combination with the deoxy-hexacoordinated wild-type form involves the dissociation of the protein ligand, NO binding is slower than for the related mutants. Structural and kinetic characteristics of neuroglobin and its mutants are analyzed. NO production in rapidly growing E. coli cell cultures is discussed.

Temperature dependent EPR measurements on copper doped Rb2ZnCl4 single crystals allowed us to evidence and study the P2(1)cn ClcI structural phase transition that takes place in this compound at 74.6 K. From the two types Of Cu2+ centers localized at different anionic sites, called Cu2+(I) and Cu2+(II), which are formed in this compound, only the Cu2+(II) centers exhibit observable changes in their EPR spectra, attributable to the symmetry lowering. The observed changes have been related to the soft-mode responsible for the structural phase transition. (C) 2003 Elsevier Ltd. All rights reserved.

The ferric form of the wild-type mouse neuroglobin (Ngb), a newly discovered heme protein which is primarily expressed in the brain of mammals, has been characterized by electron paramagnetic resonance (EPR) spectroscopy. The study reveals the simultaneous presence of two related structural forms in a wide range of pH values. The dominant low-spin form (>90%) with g-tensor principal values 3.15, 2.16 and 1.34 can be attributed to a His-Fe-III-His configuration. The high-spin form with g(perpendicular to) = 5.97 and g(parallel to) similar to 2, can be ascribed either to a hexacoordinated His-Fe-III-H2O form or to a pentacoordinated His-Fe-III. The high-spin to low-spin ratio is found to decrease with increasing pH values. (C) 2002 Elsevier Science B.V. All rights reserved.

High-resolution electron microscopy (HREM) studies of the microstructure and specific defects in hexagonal boron nitride (h-BN) precursors and cubic boron nitride (c-BN) crystals made under high-pressure high-temperature conditions revealed the presence of half-nanotubes at the edges of the h-BN particles. Their sp(3) bonding tendency could strongly influence the nucleation rates of c-BN. The atomic resolution at extended dislocations was insufficient to allow us to determine the stacking fault energy in the c-BN crystals. Its mean value of 191 +/- 15 mJ m(-2) is of the same order of magnitude as that of diamond. High-frequency (94 GHz) electron paramagnetic resonance studies on c-BN single crystals have produced new data on the D1 centres associated with the boron species. Ion-beam-induced luminescence measurements have indicated that c-BN is a very interesting luminescent material, which is characterized by four luminescence bands and exhibits a better resistance to ionizing radiation than CVD diamond.

Tl-0 (6 p(1)) irradiation centers are proposed as new paramagnetic probes for structural phase transition investigations. The P2(1)cn --> C1 c1 phase transition in Rb-2 ZnCl4 single crystals is monitored using the Tl-0 and the well-known Tl2+ (6 s(1)) paramagnetic probes. The anomalous temperature dependence exhibited by the EPR spectra of both types of centers in the C1 c1 phase was analyzed considering a soft mode contribution.

An Fe+-type center with axial (001) symmetry has been studied by electron nuclear double resonance (ENDOR) in the microwave X and Q bands. The Fe+(I) center is produced only after irradiation with x or gamma rays at 80 K of SrCl2:Fe2+ crystals grown in a Cl-2 atmosphere. It has a 3d(7) F-4 Gamma (8) ground state with spin S =3/2. As shown by the correlated analysis of the ENDOR data and electron paramagnetic resonance superhyperfine structure, the Fe+ ion is situated in the center of a tetragonally compressed cube of eight nearest Cl- ions. The simplest model of the Fe+(I) center, compatible with the magnetic resonance results, consists of an interstitial Fe+ ion with two substitutional monovalent cations, very likely K+ ions, in two opposite nearest-neighbor Sr2+ sites along the tetragonal axis of the center.

The W-band (95 GHz) ODMR spectra of AgCl nanocrystals (NCs) embedded in a KCl single crystal lattice have been measured for various orientations of the magnetic field in a 100} crystal plane, Only self-trapped exciton (STE) signals are observed while no ODMR is found from distant electron-hole pairs. This confirms the conclusion of a previous ODMR study in the Q-band (at 35 GHz) concerning the spatial confinement effect and impurity exclusion on exciton recombination in NCs of AgCl. Through increased resolution, more accurate g- and zero-field splitting values of the triplet state were obtained in good agreement with those of the STE in bulk AgCl.

The results of a low-temperature study by high frequency (94 GHz) EPR on brown-to-dark colored single crystals selected from cBN crystalline powders prepared by the HPHT technique with boron excess, are presented. Previous investigations by low frequency (9.4 GHz) EPR spectroscopy on such dark polycrystalline c-BN powders resulted in the identification of two paramagnetic species D1 and D2 associated with the brown-to-dark coloration, the spectrum of the latter one being observed only above 100 K. The present research identifies the D1 species, studied by EPR at low temperatures, as consisting mainly from anisotropic paramagnetic centers with electron spin S = 1/2, local symmetry axis along one of the crystal [111] axes and principal g values g(parallel to) = 2.0032 +/- 0.0009 and g(perpendicular to) = 2.0094 +/- 0.0005 at T = 10 K. (C) 2001 Elsevier Science B.V. All rights reserved.

Several Tl-0 (6s(2)6p(1))-type paramagnetic centers, produced by low temperature X-ray irradiation, were observed and studied by electron spin resonance (ESR) in the orthorhombic ferroelectric phase of thallium doped Rb2ZnCl4 crystals. The centers were formed by electron trapping at Tl+ ions localized substitutionally at Rb+ sites. The number and properties of the observed centers account for the tripling of the unit cell in the ferroelectric phase.

Dark-brown crystalline powders and selected single crystals of cubic boron nitride grown by the HP-HT method, with boron excess, have been studied in a broad temperature range by electron spin resonance (ESR) in the X and W microwave frequency bands, respectively. The X-band spectra consist of two superimposed lorentzian components attributed to two types of related paramagnetic defects called D1 and D2, respectively. According to the W-band data, the D I centre exhibits local axial symmetry and ground spin state S = 1/2, with g(parallel to) = 2,0033 and g(perpendicular to) = 2.0094 at T = 10 K. The broad D2 line, observed only in the X-band, at g = 2.0084, at higher temperatures, seems to result from transitions inside the excited levels of another boron related defect.

Previous Electron Paramagnetic Resonance (EPR) studies have shown that Fe2+ doped SrCl2 crystals grown in a chlorine atmosphere exhibit new trapped electron Fe+ centers after irradiation with X or gamma-rays at 77 K. Two types of such centers, called Fe+ (I) and Fe+ (II), both exhibiting axial [001] symmetry, have been identified. We present here the results of an Electron Nuclear Double Resonance (ENDOR) study in X and Q-band on the Fe+ (I) center, which has been found to be thermally stable up to 700K. The superhyperfine and quadrupole interactions of the paramagnetic Fe+ ion with the nearest Cl- ions have been determined from the ENDOR angular dependence data. The results strongly suggest that the Fe+ (I) center consists of a Fe+ ion in the center of a cube of eight Cl- ions, compressed along an[001] direction.

Using the new ion beam-induced luminescence (IBIL) apparatus in National Legnaro Laboratories, Italy, a series of measurements concerning both wide-area luminescence spectra and monochromatic luminescence maps with a space resolution of a few mum has been carried out on several CVD diamond and c-BN samples. Protons of 2 MeV with a penetration depth of approximately 25 mum have been used in order to investigate the materials in the bulk. These measurements have been correlated with particle-induced X-ray emission (PIXE) and EPR data. The measurements have been performed at increasing proton doses in order to also investigate the radiation hardness of luminescence peaks. The results indicate that ionoluminescence of CVD diamond is dominated by three bands at approximately 2, 2.4 and 2.9 eV, with the intermediate band being very radiation-hard, and the other two radiation-weak. The band at 2 eV is correlated with N content, and is particularly high in samples with poor electronic properties. IBIL in c-BN is also dominated by three bands, one at approximately 2 eV, and the other two at higher energies with respect to CVD diamond. All these three bands seem to be relatively radiation-hard with respect to CVD diamond, and to be related to defects induced by doping. (C) 2001 Elsevier Science B.V. All rights reserved.

Relations between the concentrations of neutral (N-0) and charged (N+) single-substitutional nitrogen and of nitrogen-vacancy (N-V) complexes in chemical vapour deposited diamond films of approximate to 0.2 mm thickness with nitrogen impurity concentration levels of 10 ppm are studied. For this purpose the films were subjected to 8 MeV electron irradiation at room temperature and subsequent annealing at 800 degrees C. The samples were analysed by micro-photoluminescence; visible and IR absorption, and Electron Spin Resonance techniques. It was found that the concentration of nitrogen in the (N-V) and N+ forms, in as-grown films, is less than 0.1% and 10% of the neutral substitutional nitrogen N-0, respectively.

The presence and concentration of nitrogen and hydrogen impurities in thick diamond films grown by microwave plasma chemical vapor deposition at various H-2 gas flow rates, keeping a constant [CH4]:[H-2]=2.5% concentration ratio, have been determined by electron spin resonance and optical absorption spectroscopy. The relative concentration of both impurities, present as paramagnetic atomic species with different relaxation properties, has been found by ESR measurements to decrease exponentially with the increase in the H-2 gas flow rate. Moreover, the resulting values were proportional to the content of substitutional nitrogen and CHx groups obtained from infrared and ultraviolet-visible optical absorption measurements, respectively. The decrease in the concentration of both impurities with an increase in the quality of the studied diamond films, early observed from high resolution electron microscopy studies on the same samples, strongly suggests that the incorporation of both impurities, as paramagnetic atomic species, is directly related to the concentration of the extended lattice defects. (C) 2000 American Institute of Physics. [S0021- 8979(00)08611-4].

A correlated ESR and optical emission study on samples doped with different concentrations of Tl+ impurity ions shows the involvement of paramagnetic Pb-2(3+) self-trapped electron centers (STEL) and trapped hole A centers in the electron-hole recombination responsible for the 2.6 eV blue-green luminescence. (C) 2000 Elsevier Science B.V. All rights reserved.

An X-band electron paramagnetic resonance (EPR) study of nominally pure, diamond-like cubic boron nitride (c-BN) crystalline powders, has led to the first identification of a spectrum attributed to two related paramagnetic species. The composite EPR spectrum can be observed only in dark brown colored powders known to contain excess of boron. It consists of two superimposed lorentzian components, called D1 and D2, centered at g1 = 2.0063 and g2 = 2.0084, with peak-to-peak linewidths of 3.3 and 17.9 mT, respectively. The temperature dependence of the integrated intensities, their linewidths and intensity ratio D2/D1 allows one to conclude that the narrow line D1 originates from EPR transitions inside a S = 1/2 ground doublet and the broad line D2 from transitions inside the excited levels of another center. Evidence suggests that both centers are boron related paramagnetic species. (C) 2000 Elsevier Science Ltd. All rights reserved.

ESR measurements in the 9 and 94 GHz microwave frequency bands were performed on thick free-standing polycrystalline diamond films grown by microwave plasma enhanced CVD from CH4/H-2 mixtures under variable deposition conditions. An exponential decrease in the concentration of the N-0 centres with increase in the H-2 flow rate was found. Neither H1 nor H2 centres could be detected.

Two Fe+ centres have been identified by ESR after X-ray irradiation at 80 K of chlorinated SrCl2 : Fe2+ crystals. Both centres, with tetragonal symmetry, consist of an Fe+ ion with a neighbouring charged defect along the [001] symmetry axis. The substitutional Fe+ ion of the Fe+(I) centre is strongly off-centre displaced in the Fe+(II) centres, in the middle of a square of four nearest neighbour chlorine ligands.

Tl2+(6s(1))-type of paramagnetic centres, produced by low temperature X-ray irradiation, were observed in the low temperature ferroelectric phases of Rb2ZnCl4 : TICl crystals. The difference between the spin-Hamiltonian parameters of the main centre, determined in the two phases, is attributed to the symmetry lowering at phase transition.

Cubic boron nitride (c-BN) crystals synthesised at high pressures and temperatures are analysed by optical microscopy, transmission electron microscopy, electron diffraction and electron spin resonance. For various growth conditions, the results of these studies indicate that the c-BN crystals contain defects and impurities. This is the first time that dislocation cores have been revealed in c-BN at the atomic level. Atomic resolution at extended dislocations allows us to determine the stacking-fault energy in c-BN, yielding a mean value of 191+/-15 mJ m(-2). This value, which is reported for the first time for c-BN, is of the same order of magnitude as in diamond. (C) 1999 Elsevier Science S.A. All rights reserved.

High-quality single crystals of Rb2ZnCl4 and K2ZnCl4, pure or doped with Cu, Mn, Cd, Tl, Sn, Pb and In cations, were grown by Czochralski technique in argon atmosphere, using an experimental setup that allows direct visual access to the whole growth zone. Slowly cooled crystals exhibit excellent cleavage properties. Fastly cooled crystals do cleave poorly. As shown by X-ray diffraction studies, such K2ZnCl4 samples exhibit inclusions of the high-temperature Pmcn phase with lattice parameters a = 7.263(2) Angstrom, b = 12.562(2) Angstrom and c = 8.960(4) Angstrom in the P2(1) cn room temperature stable phase. ESR and optical spectroscopy studies revealed the localization and valence state of the cation dopants. (C) 1999 Elsevier Science B.V. All rights reserved.

Chlorinated SrCl2:Fe2+ crystals exhibit, after X-ray irradiation, two trapped-electron Fe+(I) and Fe+(II) centers both with axial [001] symmetry, but different EPR spectrum parameters and production properties. The analysis of the experimental data strongly suggests a substitutional eight-fold coordination of the Fe+ ion in the Fe+(I) center and a strong [001] off-center displacement to a fourfold coordinated site in the Fe+(II) center resulting in S = 3/2 and S = 1/2 ground states, respectively.

An EPR study of the Tl+-doped PbCl2 crystals x-ray irradiated at low temperature reveals the presence, besides known spectra attributed to hole-trapped Tl2+ centers and Pb-2(3+) self-trapped-electron (STEL) centers, of an additional strongly anisotropic set of lines consisting of an intense doublet and several weaker satellite lines spread over a large magnetic-field range. The quantitative analysis of the EPR spectrum shows the corresponding paramagnetic center to be a bent molecular ion (PbTl)(2+) resulting from electron trapping at a pair of substitutional Pb2+ and Tl+ ions. Its formation suggests the electron trapping at pairs of neighboring cations is a more general characteristic of this material, with possible relevance in photolysis and exciton localization properties.

Formation of primary paramagnetic point defects under low temperature X-ray irradiation have been studied by ESR and optical absorption in pure and thallium doped PbCl2 single crystals. Besides Pb-2(3+) self-trapped electron (STEL) centers the PbCl2 : Tl crystals exhibit trapped-electron (PbTl)(+)-type centers. Based on production properties of paramagnetic centers it is suggested that besides forming Tl-2 divided by centers the holes are self trapped at pairs of neighbouring Cl- anions resulting in V-k type centers with various orientation and length of the Cl-Cl axis. (C) 1998 Published by Elsevier Science B.V. All rights reserved.

An EPR study of SrCl2:Fe2+ crystals grown in chlorine reveals the presence after X-ray irradiation, besides the trapped-hole Fe-cub(3+) center with cubic symmetry previously observed in crystals grown under argon, of a new Fe-trig(3+) center with axial [111] symmetry. The quantitative analysis of the strongly anisotropic X-and Q-band spectra resulted in a g = 2.0141 value and zero-held-splitting parameters B-2(0) = 800.6, B-4(0) = -0.44, B-4(-3) = -10.5 and B-4(3) = 0.33 (at T = 12 K, in 10(-4) cm(-1) units). The very large B-2(0) value is attributed to the presence of a charged defect replacing one of the eight nearest neighbor Cl- ligands accompanied by an off-center displacement of the Fe3+ ion towards it. (C) 1997 Elsevier Science Ltd.

Electron spin resonance and optical studies reveal the presence of both Cu2+ and Cu+ centers in Rb2ZnCl4:Cu single crystals grown from melt and their conversion by X- or gamma-irradiation. Two types of paramagnetic Cu2+ centers with different concentrations and production properties have been identified. The more abundant Cu2+(I) center consists of a Cu2+ ion substituting for Zn2+ at the center of a ZnC42- tetrahedron. The less abundant Cu2+(II) center seems to be situated at a Rb site. Production experiments strongly suggest that during the crystal growth copper enters the Rb2ZnCl4 lattice as Cu2+, mainly at Zn2+ sites, part of it being afterwards converted to Cu+ precursor centers. The presence of a neighboring-charge compensating anion vacancy and its departure during the radiolytic Cu+(I) --> Cu2+(I) conversion seems to play an essential role in the stabilization of the Cu+(I) and Cu2+(I) centers, respectively.

This paper describes the growth of CdF2 single crystals using the Bridgman method. Unwanted vapour reactions are avoided by using an argon atmosphere and glassy carbon crucibles. The installation for the growth of CdF2 single crystals is described in detail. Optical absorption of CdF2 crystals is shown for wavelengths of 200 to 800 nm. Transmission spectrum in the 2.5-10-mu-m range shows a low level of impurities which do not affect the optical qualities.