Magnetic Properties of Fe/Cu Codoped ZnO Nanocrystals

Free-standing ZnO nanocrystals simultaneously doped with Fe and Cu with varying Fe/Cu compositions have been synthesized using colloidal methods with a mean size of similar to 7.7 nm. Interestingly, while the Cu-doped ZnO nanocrystal remains diamagnetic and Fe-doped samples show antiferromagnetic interactions between Fe sites without any magnetic ordering down to the lowest temperature investigated, samples doped simultaneously with Fe and Cu show a qualitative departure in exhibiting ferromagnetic interactions, with suggestions of ferromagnetic order at low temperature. XAS measurements establish the presence of Fe2+ and Fe3+ ions, with the concentration of the trivalent species increasing in the presence of Cu doping, providing direct evidence of the Fe2+ + Cu2+ sic Fe3+ + Cu+ redox couple being correlated with the ferromagnetic property. Using DFT, the unexpected ferromagnetic nature of these systems is explained in terms of a double exchange between Fe atoms, mediated by the Cu atom, in agreement with experimental observations.

Interaction of CdSe and ZnO nanocrystals with electron-donor and -acceptor molecules

Interaction of CdSe and ZnO nanocrystals with electron-donating tetrathiafulvalene (TTF) and electron-withdrawing tetracyanoethylene (TCNE) has been investigated. Isothermal calorimetry shows CdSe nanocrystals interact more strongly with TCNE than TTF. Interaction of larger CdSe nanocrystals with TCNE causes a red-shift in the band-edge emission because of agglomeration, while the smaller CdSe nanocrystals, exhibiting stronger interaction with TCNE modify the optical gap of the nanocrystal. Luminescence of CdSe gets quenched sharply after addition of both TTF and TCNE. ZnO nanocrystals also exhibit luminescence quenching to lesser extent. Defect-emission of ZnO nanocrystals gets red or blue-shifted after interaction with TTF or TCNE respectively. (C) 2012 Elsevier B. V. All rights reserved.

Cadmium deoxycholate: a new and efficient precursor for highly luminescent CdSe nanocrystals

We have demonstrated that cadmium deoxycholate (1), a Cd-salt, provides a convenient and inexpensive route to high quality CdSe nanocrystals with photoluminescence (PL) in the blue to red region of the visible spectrum, with reproducible quantum yields as high as similar to 47%. Owing to the high thermal stability of the bile acid based cadmium precursor (decomposition point: 332 degrees C), it was possible to achieve high injection and growth temperatures (similar to 300 degrees C) for the nanocrystals, which was essential for obtaining larger CdSe nanocrystals emitting in the red region (625-650 nm) with a sharp full width at half maximum (FWHM) (23 nm) and multiple (6-7) excitonic absorption features. The as-prepared CdSe nanocrystals synthesized from cadmium deoxycholate represent a series of highly efficient emitters with pure colours and controllable sizes, shapes and structures.

Thermoelectric properties of PbTe with encapsulated bismuth secondary phase

Lead Telluride (PbTe) with bismuth secondary phase embedded in the bulk has been prepared by matrix encapsulation technique. X-Ray Diffraction results indicated crystalline PbTe, while Rietveld analysis showed that Bi did not substitute at either Pb or Te site, which was further confirmed by Raman and X-Ray Photoelectron Spectroscopy. Scanning Electron Microscopy showed the expected presence of a secondary phase, while Energy Dispersive Spectroscopy results showed a slight deficiency of tellurium in the PbTe matrix, which might have occurred during synthesis due to higher vapor pressure of Te. Transmission Electron Microscopy results did not show any nanometer sized Bi phase. Seebeck coefficient (S) and electrical conductivity (sigma) were measured from room temperature to 725 K. A decrease in S and sigma with increasing Bi content showed an increased scattering of electrons from PbTe-Bi interfaces, along with a possible electron acceptor role of Bi secondary phase. An overall decrease in the power factor was thus observed. Thermal conductivity, measured from 400K to 725K, was smaller at starting temperature with increasing Bi concentration, and almost comparable to that of PbTe at higher temperatures, indicating a more important role of electrons as compared to phonons at PbTe-Bi interfaces. Still, a reasonable zT of 0.8 at 725K was achieved for undoped PbTe, but no improvement was found for bismuth added samples with micrometer inclusions. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4796148]

Growth and characterization of micro and nanostructures of lead telluride (PbTe) by thermal evaporation method

Lead telluride micro and nanostructures have been grown on silicon and glass substrates by a simple thermal evaporation of PbTe in high vacuum of 3 x 10(-5) mbar. Growth was carried out for two different distances between the evaporation source and the substrates. Synthesized products consist of nanorods and micro towers for 2.4 cm and 3.4 cm of distance between the evaporation source and the substrates respectively. X-ray diffraction and transmission electron microscopy studies confirmed crystalline nature of the nanorods and micro towers. Nanorods were grown by vapor solid mechanism. Each micro tower consists of nano platelets and is capped with spherical catalyst particle at their end, suggesting that the growth proceeds via vapor-liquid-solid (VLS) mechanism. EDS spectrum recorded on the tip of the micro tower has shown the presence of Pb and Te confirming the self catalytic VLS growth of the micro towers. These results open up novel synthesis methods for PbTe nano and microstructures for various applications.

Ultranarrow and Widely Tunable Mn2+-Induced Photoluminescence from Single Mn-Doped Nanocrystals of ZnS-CdS Alloys

Extensively studied Mn-doped semiconductor nanocrystals have invariably exhibited photoluminescence over a narrow energy window of width <= 150 meV in the orange-red region and a surprisingly large spectral width (>= 180 meV), contrary to its presumed atomic-like origin. Carrying out emission measurements on individual single nanocrystals and supported by ab initio calculations, we show that Mn PL emission, in fact, can (i) vary over a much wider range (similar to 370 meV) covering the deep green-deep red region and (ii) exhibit widths substantially lower (similar to 60-75 meV) than reported so far, opening newer application possibilities and requiring a fundamental shift in our perception of the emission from Mn-doped semiconductor nanocrystals.

Defect induced optical bandgap narrowing in undoped SnO2 nanocrystals

Unusual optical bandgap narrowing is observed in undoped SnO2 nanoparticles synthesized by the solution combustion method. The estimated crystallite size is nearly 7 nm. Though the quantum confinement effect predicts a larger optical bandgap for materials with small crystallite size than the bulk, the optical bandgap in the as synthesized materials is found to be 2.9 eV compared to the reported value of 3.6 eV for bulk SnO2 particles. The yellow-green photoluminescence emissions and the observed narrowing of the bandgap can be attributed to the deep donor levels of oxygen vacancies, owing to the high exothermicity of the combustion reaction and the faster cooling rates involved in the process.

Controlling Light Absorption in Charge-Separating Core/Shell Semiconductor Nanocrystals

Semiconductor nanocrystals of different formulations have been extensively studied for use in thin-film photovoltaics. Materials used in such devices need to satisfy the stringent requirement of having large absorption cross sections. Hence, type-II semiconductor nanocrystals that are generally considered to be poor light absorbers have largely been ignored. In this article, we show that type-II semiconductor nanocrystals can be tailored to match the light-absorption abilities of other types of nanostructures as well as bulk semiconductors. We synthesize type-II ZnTe/CdS core/shell nanocrystals. This material is found to exhibit a tunable band gap as well as absorption cross sections that are comparable to (die. This result has significant implications for thin-film photovoltaics, where the use of type-II nanocrystals instead of pure semiconductors can improve charge separation while also providing a much needed handle to regulate device composition.

Synthesis, Characterization, and Nuclear Magnetic Resonance Study of Chitosan-Coated Mn1-xZnxFe2O4 Nanocrystals

Ultra-fine crystallites of Mn1-xZnxFe2O4 series (0 <= x <= 1) were synthesized through wet chemical co- precipitation method followed by calcination at 200 degrees C for 4 hours. Formation of ferrites was confirmed by X-ray diffraction, TEM selected area diffraction (SAD) and Fourier Transform Infra-red Spectroscopy (FTIR). Nanocrystallites of different compositions in the series were coated with biocompatible chitosan in order to investigate their possible application as contrast agent for magnetic resonance imaging (MRI). Chitosan coating examined by FTIR, revealed a strong bonding of chitosan molecules to the surface of the ferrite nanocrystallites. Spin-spin, tau(2) relaxivities of nuclear spins of hydrogen protons of the solutions for different ferrites were measured from concentration dependence of relaxation time by nuclear magnetic resonance (NMR). All the compositions of Mn1-xZnxFe2O4 series possess higher values of tau(2) relaxivity thus making them suitable as contrast agents for tau(2) weighted imaging by MRI.

Thermoelectric Properties of Two-Phase PbTe with Indium Inclusions

The thermoelectric figure of merit (zT) can be increased by introduction of additional interfaces in the bulk to reduce the thermal conductivity. In this work, PbTe with a dispersed indium (In) phase was synthesized by a matrix encapsulation technique for different In concentrations. x-Ray diffraction analysis showed single-phase PbTe with In secondary phase. Rietveld analysis did not show In substitution at either the Pb or Te site, and this was further confirmed by room-temperature Raman data. Low-magnification (similar to 1500x) scanning electron microscopy images showed micrometer-sized In dispersed throughout the PbTe matrix, while at high magnification (150,000x) an agglomeration of PbTe particles in the hot-pressed samples could be seen. The electrical resistivity (rho) and Seebeck coefficient (S) were measured from 300 K to 723 K. Negative Seebeck values showed all the samples to be n-type. A systematic increase in resistivity and higher Seebeck coefficient values with increasing In content indicated the role of PbTe-In interfaces in the scattering of electrons. This was further confirmed by the thermal conductivity (kappa), measured from 423 K to 723 K, where a greater reduction in the electronic as compared with the lattice contribution was found for In-added samples. It was found that, despite the high lattice mismatch at the PbTe-In interface, phonons were not scattered as effectively as electrons. The highest zT obtained was 0.78 at 723 K for the sample with the lowest In content.

From (Au5Sn + AuSn) physical mixture to phase pure AuSn and Au5Sn intermetallic nanocrystals with tailored morphology: digestive ripening assisted approach

Here we present digestive ripening facilitated interatomic diffusion for the phase controlled synthesis of homogeneous intermetallic nanocrystals of Au-Sn system. Au and Sn metal nanoparticles synthesized by a solvated metal atom dispersion (SMAD) method are employed as precursors for the fabrication of AuSn and Au5Sn which are Au-rich Au-Sn intermetallic nanocrystals. By optimizing the stoichiometry of Au and Sn in the reaction mixture, and by employing growth directing agents, the formation of phase pure intermetallic AuSn and Au5Sn nanocrystals could be realized. The as-prepared Au and Sn colloidal nanoparticles and the resulting intermetallic nanocrystals are thoroughly characterized by powder X-ray diffraction, transmission electron microscopy (TEM and STEM-EDS), and optical spectroscopy. The results obtained here demonstrate the potential of solution chemistry which allows synthesizing phase pure Au-Sn intermetallics with tailored morphology.

Determination of Internal Structures of Heterogeneous Nanocrystals Using Variable-Energy Photoemission Spectroscopy

This article describes the determination of the internal structure of heterogeneous nanoparticle systems including inverted core-shell (CdS core and CdSe shell) and alloyed (CdSeS) quantum dots using depth-resolved, variable-energy X-ray photoelectron spectroscopy (XPS). A unique feature of this work is the combination of photoelectron spectroscopy performed at lower X-ray energies (400-700 eV), to achieve surface sensitivity, with bulk sensitive measurements at high photon energies (>2000 eV), thereby providing detailed information about the whole nanoparticle structure with a great accuracy. The use of high photon energies furthermore allows us to investigate nanoparticles much larger than those studied thus far. This capability is a consequence of the much-increased mean free path of the photoelectron achieved at high excitation energies. Our results show that the actual structures of the synthesized nanoparticles are considerably different from the nominal, targeted structures, which can be post facto rationalized in terms of the reactivity of different constituents.

Rapid, microwave-assisted synthesis of Gd2O3 and Eu:Gd2O3 nanocrystals: characterization, magnetic, optical and biological studies

Ultra-small crystals of undoped and Eu-doped gadolinium oxide (Gd2O3) were synthesised by a simple, rapid microwave-assisted route, using benzyl alcohol as the reaction solvent. XRD, XPS and TEM analysis reveal that the as-prepared powder material consists of nearly monodisperse Gd2O3 nanocrystals with an average diameter of 5.2 nm. The nanocrystals show good magnetic behaviour and exhibit a larger reduction in relaxation time of water protons than the standard Gd-DTPA complex currently used in MRI imaging. Cytotoxicity studies (both concentration- and time-dependent) of the Gd2O3 nanocrystals show no adverse effect on cell viability, evidencing their high biological compatibility. Finally, Eu:Gd2O3 nanocrystals were prepared by a similar route and the red luminescence of Eu3+ activator ions was used to study the cell permeability of the nanocrystals. Red fluorescence from Eu3+ ions observed by fluorescence microscopy shows that the nanocrystals (Gd2O3 and Eu:Gd2O3) can permeate not only the cell membrane but can also enter the cell nucleus, rendering them candidate materials not only for MRI imaging but also for drug delivery when tagged or functionalized with specific drug molecules.

Elastic Properties Of Sulphur And Selenium Doped Ternary PbTe Alloys By First Principles

Lead telluride (PbTe) is an established thermoelectric material which can be alloyed with sulphur and selenium to further enhance the thermoelectric properties. Here, a first principles study of ternary alloys PbSxTe(1-x) and PbSexTe(1-x) (0 <= x <= 1) based on the Virtual Crystal Approximation (VCA) is presented for different ratios of the isoelectronic atoms in each series. Equilibrium lattice parameters and elastic constants have been calculated and compared with the reported data. Anisotropy parameter calculated from the stiffness constants showed a slight improvement in anisotropy of elastic properties of the alloys over undoped PbTe. Furthermore, the alloys satisfied the predicted stability criteria from the elastic constants, showing stable structures, which agreed with the previously reported experimental results.

Role of spectator ions in influencing the properties of dopant-free ZnO nanocrystals

Towards fundamental studies and potential applications, achieving precise control over the generation of defects in pure ZnO nanocrystals has been always intriguing. Herein, we explored the rote of spectator ions (Co2+ and Ni2+) in influencing the functional properties of ZnO nanocrystals. The crystalline quality, phase purity, and composition of as-prepared samples were thoroughly established by powder X-ray diffraction, electron microscopy (TEM and STEM), and by Raman and X-ray photoelectron spectroscopies (XPS). Despite the presence of Co2+ and Ni2+ ions in the reaction mixture, STEM-energy dispersive spectroscopy (EDS), XPS analysis, and inductively-coupled plasma mass spectrometry (ICP-MS) revealed that the ZnO nanocrystals formed are dopant-free. Even so, their luminescence and magnetic properties were substantially different from those of pure ZnO nanocrystals synthesized using a similar methodology. We attribute the origin of these properties to the defects associated with ZnO nanocrystals generated under different but optimized conditions.