Reversible ferromagnetic switching in ZnO:(Co,Mn) powders

We report here on the magnetic properties of ZnO:Mn- and ZnO:Co-doped nanoparticles. We have found that the ferromagnetism of ZnO:Mn can be switched on and off by consecutive low-temperature annealings in O2 and N2, respectively, while the opposite phenomenology was observed for ZnO:Co. These results suggest that different defects (presumably n-type for ZnO:Co and p-type for ZnO:Mn) are required to induce a ferromagnetic coupling in each case. We will argue that ferromagnetism is likely to be restricted to a very thin, nanometric layer at the grain surface. These findings reveal and give insight into the dramatic relevance of surface effects to the occurrence of ferromagnetism in ZnO-doped oxides.

A new chemical route to synthesise TM-doped (TM = Co, Fe) TiO2 nanoparticles

Since the discovery of ferromagnetism well above room temperature in the Co-doped TiO2 system, diluted magnetic semiconductors based on TiO2 doped with transition metals have generated great interest because of their potential use in the development of spintronic devices. The purpose of this paper is to report on a new and swift chemical route to synthesise highly stable anatase single-phase Co- and Fe-doped TiO2 nanoparticles, with dopant concentrations of up to 10 at.-% and grain sizes that range between 20 and 30 nm. Complementary structural, microstructural and chemical analyses of the different nanopowders synthesised strongly support the hypothesis that a homogeneous distribution of the dopant element in the substitutional sites of the anatase structure has been achieved. Moreover, UV/Vis diffuse reflectance spectra of powder samples show redshifts to lower energies and decreasing bandgap energies with increasing Co or Fe concentration, which is consistent with n-type doping of the TiO2 anatase matrix. Films of Co-doped TiO2 were successfully deposited onto Si (100) substrates by the dip-coating method, with suspensions of Ti1-xCOxO2 nanoparticles in ethylene glycol. ((C)Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

A systematic study of the structural and magnetic properties of Mn-, Co-, and Ni-Doped Colloidal Fe3O4 nanoparticles

A series of colloidal MxFe3-xO4 (M = Mn, Co, Ni; x = 0–1) nanoparticles with diameters ranging from 6.8 to 11.6 nm was synthesized by hydrothermal reaction in aqueous medium at low temperature (200 °C). Energy-dispersive X-ray microa-nalysis and inductively coupled plasma spectrometry confirms that the actual elemental compositions agree well with the nominal ones. The structural properties of obtained nanoparticles were investigated by using powder X-ray diffraction, Raman scattering, Mössbauer spectroscopy, and electron microscopy. The results demonstrate that our synthesis technique leads to the formation of chemically uniform single-phase solid solution nanoparticles with cubic spinel structure, confirming the intrinsic doping. Magnetic studies showed that, in comparison to Fe3O4, the saturation magnetization of MxFe3-xO4 (M = Mn, Ni) decreases with increasing dopant concentration, while Co-doped samples showed similar saturation magnetizations. On other hand, whereas Mn- and Ni-doped nanoparticles exhibits superparamagnetic behavior at room temperature, ferromagnetism emerges for CoxFe3-xO4 nanoparticles, which can be tuned by the level of Co doping.

Intermolecular energy transfer and photostability of luminescence-tuneable multicolour PMMA films doped with lanthanide-beta-diketonate complexes

It is reported in this work the preparation, characterisation and photoluminescence study of poly(methylmethacrylate) (PMMA) thin films co-doped with [Eu(tta)(3)(H(2)O)(2)] and [Tb(acac)(3)(H(2)O)(3)] complexes. Both the composition and excitation wavelength may be tailored to fine-tune the emission properties of these Ln(3+)-beta-diketonate doped polymer films, exhibiting green and red primary colours, as well as intermediate colours. In addition to the ligand-Ln(3+) intramolecular energy transfer, it is observed an unprecedented intermolecular energy transfer process from the (5)D(4) emitting level of the Tb(3+) ion to the excited triplet state T(1) of the tta ligand coordinated to the Eu(3+) ion. The PMMA polymer matrix acts as a co-sensitizer and enhances the overall luminescence intensity of the polymer films. Furthermore, it provides considerable UV protection for the luminescent species and improves the photostability of the doped system.

Oxide ionic conductivity and microstructures of Sm- or La-doped CeO2-based systems

The concept of crystallographic index termed the effective index is suggested and applied to the design of ceria (CeO2)-based electrolytes to maximize oxide ionic conductivity. The suggested index considers the fluorite structure, and combines the expected oxygen vacancy level with the ionic radius mismatch between host and dopant cations. Using this approach, oxide ionic conductivity of Sm- or La-doped CeO2-based system has been optimized and tested under operating conditions of a solid oxide fuel cell. In the observation of microstructure in atomic scale, both Sm-doped CeO2 and La-doped CeO2 electrolytes had large micro-domains over 10 nm in the lattice. On the other hand, Sm or La and alkaline earth co-doped CeO2-based electrolytes with high effective index had small micro-domains around 1-3 nm in the microstructure. The large micro-domain would prevent oxide ion from passing through the lattice. Therefore, it is concluded that the improvement of ionic conductivity is reflected in changes of microstructure in atomic scale. (C) 2002 Elsevier Science B.V. All rights reserved.

Structural, electrical and magnetic studies of Co:SnO2 and (Co,Mo):SnO2 films prepared by pulsed laser deposition

Here we report on the structural, optical, electrical and magnetic properties of Co-doped and (Co,Mo)-codoped SnO2 thin films deposited on r-cut sapphire substrates by pulsed laser deposition. Substrate temperature during deposition was kept at 500 degrees C. X-ray diffraction analysis showed that the undoped and doped films are crystalline with predominant orientation along the [1 0 1] direction regardless of the doping concentration and doping element. Optical studies revealed that the presence of Mo reverts the blue shift trend observed for the Co-doped films. For the Co and Mo doping concentrations studied, the incorporation of Mo did not contribute to increase the conductivity of the films or to enhance the ferromagnetic order of the Co-doped films. (C) 2012 Elsevier B.V. All rights reserved.

Phase growth control in low temperature PLD Co: TiO2 films by pressure

This paper reports on the structural and optical properties of Co-doped TiO2 thin films grown onto (0001)Al2O3 substrates by non-reactive pulsed laser deposition (PLD) using argon as buffer gas. It is shown that by keeping constant the substrate temperature at as low as 310 degrees C and varying only the background gas pressure between 7 Pa and 70 Pa, it is possible to grow either epitaxial rutile or pure anatase thin films, as well as films with a mixture of both polymorphs. The optical band gaps of the films are red shifted in comparison with the values usually reported for undoped TiO2, which is consistent with n-type doping of the TiO2 matrix. Such band gap red shift brings the absorption edge of the Co-doped TiO2 films into the visible region, which might favour their photocatalytic activity. Furthermore, the band gap red shift depends on the films' phase composition, increasing with the increase of the Urbach energy for increasing rutile content. (C) 2012 Elsevier B.V. All rights reserved.

Undoped and calcium doped borate glass system for thermoluminescent dosimeter

Borate glasses present an absorption coefficient very close to that of human tissue. This fact makes some borates ideal materials to develop medical and environmental dosimeters. Glass compositions with calcium tetraborate (CaB4O7) and calcium metaborate (CaB2O4), such as the xCaB(4)O(7) - (100-x)CaB2O4 System (0 <= x <= 100 wt%) were obtained by the traditional melting/quenching method. A phenomenon widely known as the 'boron anomaly' was observed in our thermal analysis measurements, as indicated by the increase of T, and the appearance of a maximum value in the composition with 40 wt% of CaB2O4. The Dy doped and Li co-doped 80CaB(4)O(7)-20CaB(2)O(4) (Wt%) glass samples were studied by the thermoluminescence technique. The addition of Dy improved the signal sensitivity in about three times with respect to the undoped glass sample. The addition of Li as a co-dopant in this glass caused a shift to a lower temperature of about 20 degrees C in the main glow peak. The structural analysis of the 80CaB(4)O(7)-20CaB(2)O(4) (wt%) undoped and doped samples were studied through infrared absorption. We have noted an increase in the coordination number of the boron atoms from 3 to 4, i.e., the conversion of the BO3 triangular structural units into BO4 tetrahedra. (c) 2006 Elsevier B.V. All rights reserved.

Influence of thermal annealing treatment in oxygen atmosphere on grain boundary chemistry and non-ohmic properties of SnO2 center dot MnO polycrystalline semiconductors

The present work studied the influence of thermal treatment in oxygen rich atmosphere on heterogenous junctions in Mn-doped SnO2 polycrystalline system presenting varistor behavior. The samples were prepared by conventional oxide mixture methodology, and were submitted to heat treatment in oxygen rich atmosphere at 900 degrees C for 2h. The samples were characterized by X-ray diffraction, scanning electron microscopy, dc and ac electrical measurements. The results showed that there is an evident relationship between the microstructure heterogeneity and non-ohmic electrical properties. It was found that for this SnO2 center dot MnO-based varistor system the heat treatment in oxygen rich atmosphere does not necessarily increase the varistors properties, which was related to the decrease in the grain boundary resistance. The results are compared with Co-doped SnO2 varistors and ZnO based varistors. (C) 2008 WILEY-VCH Verlay GmbH & Co. KGaA, Weinheim.

Effect of In concentration in the starting solution on the structural and electrical properties of ZnO films prepared by the pyrosol process at 450 degrees C

Undoped and indium-doped Zinc oxide (ZnO) solid films were deposited by the pyrosol process at 450 degrees C on glass substrates From solutions where In/Zn ratio was 2, 5, and 10 at.%. Electrical measurements performed at room temperature show that the addition of indium changes the resistance of the films. The resistivities of doped films are less than non-doped ZnO films by one to two orders of magnitude depending on the dopant concentration in the solution. Preferential orientation of the films with the c-axis perpendicular to the substrate was detected by X-ray diffraction and polarized extended X-ray absorption fine structures measurements at the Zn K edge. This orientation depends on the indium concentration in the starting solution. The most textured films were obtained for solutions where In/Zn ratio was 2 and 5 at.%. When In/Zn = 10 at.%, the films had a nearly random orientation of crystallites. Evidence of the incorporation of indium in the ZnO lattice was obtained from extended X-ray absorption fine structures at the In and Zn K edges. The structural analysis of the least resistive film (Zn/In = 5 at.%) shows that In substitutes Zn in the wurtzite structure. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Nanostructure and properties of ZnO films produced by the pyrosol process

Indium doped ZnO films were deposited by the pyrosol process on glass substrates at different temperatures from solutions containing In/Zn molar ratios up to 10%. The nanostructure of the films was investigated using grazing-incidence small angle X-ray scattering (GISAXS). The mass density was determined by X-ray reflectivity and the composition by X-ray photoelectron spectroscopy. The GISAXS measurements revealed an anisotropic pattern for films deposited at 573 and 623 K and a isotropic one for those deposited at higher temperatures. The anisotropic patterns indicate the presence of elongated nanopores with their long axes perpendicular to the film surface. In contrast, the isotropic nature of GISAXS patterns of films grown at high temperatures (673 and 723 K) suggests the presence of spherical voids. The pore size distribution function determined from the isotropic patterns indicates a multimodal size distribution. on the other hand, the measured mass density of the doped films with isotropic nanotexture is higher than that of the anisotropic films while the electric resistivity is significantly lower. This is in agreement with the detected strong reduction of the void density and specific surface area at approximately constant pore size.

Effect of in concentration in the starting solution on the structural and electrical properties of ZnO films prepared by the pyrosol process at 450°C

Undoped and indium-doped Zinc oxide (ZnO) solid films were deposited by the pyrosol process at 450°C on glass substrates from solutions where In/Zn ratio was 2, 5, and 10 at.%. Electrical measurements performed at room temperature show that the addition of indium changes the resistance of the films. The resistivities of doped films are less than non-doped ZnO films by one to two orders of magnitude depending on the dopant concentration in the solution. Preferential orientation of the films with the c-axis perpendicular to the substrate was detected by X-ray diffraction and polarized extended X-ray absorption fine structures measurements at the Zn K edge. This orientation depends on the indium concentration in the starting solution. The most textured films were obtained for solutions where In/Zn ratio was 2 and 5 at.%. When In/Zn = 10 at.%, the films had a nearly random orientation of crystallites. Evidence of the incorporation of indium in the ZnO lattice was obtained from extended X-ray absorption fine structures at the In and Zn K edges. The structural analysis of the least resistive film (Zn/In = 5 at.%) shows that In substitutes Zn in the wurtzite structure. © 2000 Elsevier Science B.V. All rights reserved.

Blue upconversion enhancement by a factor of 200 in Tm 3+-doped tellurite glass by codoping with Nd 3+ ions

We investigated near-infrared-to-blue upconversion from thulium (Tm 3+) doped in tellurite glasses upon continuous wave excitation near 800 nm. We observed an enhancement of over two orders of magnitude of the upconverted emission at ∼480nm when neodymium (Nd 3+) ions were codoped with Tm 3+ ions. For comparison, using a Tm 3+:Nd 3+ codoped fluorozirconate glass as a reference material we observed a 40-fold enhancement of the blue emission. Analysis of the blue emission for samples with different doping levels of Nd 3+ ions showed that energy transfer between Nd 3+ and Tm 3+ is the mechanism responsible for the enhancement in upconversion. © 2002 American Institute of Physics. © 2002 American Institute of Physics.

Tuning Low-Spin to High-Spin Mn Pairs in 2-D ZnO by Injecting Holes

We have performed an ab initio theoretical investigation of substitutional Mn(Zn) atoms in planar structures of ZnO, viz., monolayer [(ZnO)(1)] and bilayer [(ZnO)(2)] systems. Due to the 2-D quantum confinement effects, in those Mn -doped (ZnO)(1) and (ZnO)(2) structures, the antiferromagnetic (AFM) coupling between (nearest neighbor) Mn(Zn) impurities have been strengthened when compared with the one in ZnO bulk systems. On the other hand, we find that the magnetic state of these systems can be tuned from AFM to FM by adding holes, which can be supplied by a p-type doping or even photoionization processes. Whereas, upon addition of electrons (n-type doping), the system keeps its AFM configuration.

Structural and magnetic characterization of colloidal CdMnS

This paper reports on the synthesis (chemical co-precipitation reaction) and characterization (X-ray diffraction, magnetization, and electron paramagnetic resonance) of nanosized Cd1-xMnxS particles with manganese concentration up to x = 0.73. Though the literature reports that nanosized (bulk) CdS can incorporate as much as 30% (50%) of manganese ion within its crystal structure we found manganese segregation at the nanoparticle surface at doping levels as low as 14%. We found that both XRD and magnetization data support the presence of the Mn3O4 phase (observed spin-glass transition around 43 K) at the high manganese doping levels whereas the EPR data strongly suggest preferential incorporation of manganese at the nanoparticle's surface, even at low manganese doping levels. Analyses of the experimental data strongly suggest the preparation of well-defined core/shell (Cd1-xMnxS/Mn3O4) structures at higher levels of manganese doping.