Porosity of core-shell nanoparticles

The porosity of titania and zirconia covered Ag and Au nanoparticles has been investigated using the metal core reactivity as a probe. The presence of pores was confirmed by a newly discovered reaction between halocarbons and core-shell nanoparticles, in which the core gets converted into ions, which are leached out through the shell. Halocarbons having different alkyl chain lengths react with metal cores at different rates due to the differences in the accessibility of the core. It is also observed that the electrochemical accessibility of the core can be reduced by blocking the pores by adsorbates such as cis-dithiocyanato-bis(2,2'-bipyridyl-4,4'- dicarboxylic acid)ruthenium(II) dye (popularly called N3 dye). With the adsorbed dye molecules on the oxide shell, metal cores are stable for extended periods of time even after the addition of halocarbons. The porosity of the Au@SiO2 system, in which a silica shell is formed over the metal clusters through monolayers, has also been studied. Our studies show that the porosity of different kinds of shells is largely similar, allowing molecular and ion penetration

Anomalous pressure effect on the remanent lattice striction of a (La,Pr)1.2_{1.2}Sr1.8_{1.8}Mn2_{2}O7_{7} bilayered manganite single crystal

We have studied the pressure effect on magnetostriction, both in the $ab$-plane and along the c-axis, of a (La,Pr)$_{1.2}$Sr$_{1.8}$Mn$_{2}$O$_{7}$ bilayered manganite single crystal over the temperature region where the field-induced ferromagnetic metal (FMM) transition takes place. For comparison, we have also examined the pressure dependence of magnetization curves at the corresponding temperatures. The applied pressure reduces the critical field of the FMM transition and it enhances the remanent magnetostriction. An anomalous pressure effect on the remanent lattice relaxation is observed and is similar to the pressure effect on the remanent magnetization along the c-axis. These findings are understood from the view point that the double-exchange interaction driven FMM state is strengthened by application of pressure.Comment: 7 pages,7 figure

Steplike Lattice Deformation of Single Crystalline (La0.4_{0.4}Pr0.6_{0.6})1.2_{1.2}Sr1.8_{1.8}Mn2_{2}O7_{7} Bilayered Manganite

We report a steplike lattice transformation of single crystalline (La$_{0.4}$Pr$_{0.6}$)$_{1.2}$Sr$_{1.8}$Mn$_{2}$O$_{7}$bilayered manganite accompanied by both magnetization and magnetoresistive jumps, and examine the ultrasharp nature of the field-induced first-order transition from a paramagnetic insulator to a ferromagnetic metal phase accompanied by a huge decrease in resistance. Our findings support that the abrupt magnetostriction is closely related to an orbital frustration existing in the inhomogeneous paramagnetic insulating phase rather than a martensitic scenario between competing two phases.Comment: 5 pages,4figures, v4: figures are changed, in press in Phys.Rev.Let

Ferromagnetism at 300 K in spin-coated anatasea and rutile Ti0.95Fe0.05O2 films

Thin films of Ti1-xFexO2 (x=0 and 0.05) have been prepared on sapphire substrates by spin-on technique starting from metal organic precursors. When heat treated in air at 550 and 700 degrees C respectively, these films present pure anatase and rutile structures as shown both by X-ray diffraction and Raman spectroscopy. Optical absorption indicate a high degree of transparency in the visible region. Such films show a very small magnetic moment at 300 K. However, when the anatase and the rutile films are annealed in a vacuum of 1x10-5 Torr at 500 degrees C and 600 degrees C respectively, the magnetic moment, at 300 K, is strongly enhanced reaching 0.46 $\mu$B/Fe for the anatase sample and 0.48 $\mu$B/Fe for the rutile one. The ferromagnetic Curie temperature of these samples is above 350 K.Comment: 13 october 200

Ferromagnetism in defect-ridden oxides and related materials

The existence of high-temperature ferromagnetism in thin films and nanoparticles of oxides containing small quantities of magnetic dopants remains controversial. Some regard these materials as dilute magnetic semiconductors, while others think they are ferromagnetic only because the magnetic dopants form secondary ferromagnetic impurity phases such as cobalt metal or magnetite. There are also reports in d0 systems and other defective oxides that contain no magnetic ions. Here, we investigate TiO2 (rutile) containing 1 - 5% of iron cations and find that the room-temperature ferromagnetism of films prepared by pulsed-laser deposition is not due to magnetic ordering of the iron. The films are neither dilute magnetic semiconductors nor hosts to an iron-based ferromagnetic impurity phase. A new model is developed for defect-related ferromagnetism which involves a spin-split defect band populated by charge transfer from a proximate charge reservoir in the present case a mixture Fe2+ and Fe3+ ions in the oxide lattice. The phase diagram for the model shows how inhomogeneous Stoner ferromagnetism depends on the total number of electrons Ntot, the Stoner exchange integral I and the defect bandwidth W; the band occupancy is governed by the d-d Coulomb interaction U. There are regions of ferromagnetic metal, half-metal and insulator as well as nonmagnetic metal and insulator. A characteristic feature of the high-temperature Stoner magnetism is an an anhysteretic magnetization curve which is practically temperature independent below room temperature. This is related to a wandering ferromagnetic axis which is determined by local dipole fields. The magnetization is limited by the defect concentration, not by the 3d doping. Only 1-2 % of the volume of the films is magnetically ordered.Comment: 22 pages, 6 figure

Magneto-optical investigation of the field-induced spin-glass insulator to ferromagnetic metallic transition of the bilayer manganite (La0.4_{0.4}Pr0.6_{0.6})1.2_{1.2}Sr1.8_{1.8}Mn2_2O7_7

We measured the magneto-optical response of (La$_{0.4}$Pr$_{0.6}$)$_{1.2}$Sr$_{1.8}$Mn$_2$O$_7$ in order to investigate the microscopic aspects of the magnetic field driven spin-glass insulator to ferromagnetic metal transition. Application of a magnetic field recovers the ferromagnetic state with an overall redshift of the electronic structure, growth of the bound carrier localization associated with ferromagnetic domains, development of a pseudogap, and softening of the Mn-O stretching and bending modes that indicate a structural change. We discuss field- and temperature-induced trends within the framework of the Tomioka-Tokura global electronic phase diagram picture and suggest that controlled disorder near a phase boundary can be used to tune the magnetodielectric response. Remnants of the spin-glass insulator to ferromagnetic metallic transition can also drive 300 K color changes in (La$_{0.4}$Pr$_{0.6}$)$_{1.2}$Sr$_{1.8}$Mn$_2$O$_7$.Comment: 9 pages, 8 figure

Magnetic order in double-layer manganites (La(1-z)Pr(z))1.2Sr1.8Mn2O7: intrinsic properties and role of the intergrowths

We report on an investigation of the double-layer manganite series (La(1-z)Pr(z))1.2Sr1.8Mn2O7 (0 <= z <= 1), carried out on single crystals by means of both macroscopic magnetometry and local probes of magnetism (muSR, 55Mn NMR). Muons and NMR demonstrate an antiferromagnetically ordered ground state at non-ferromagnetic compositions (z >= 0.6), while more moderate Pr substitutions (0.2 <= z <= 0.4) induce a spin reorientation transition within the ferromagnetic phase. A large magnetic susceptibility is detected at {Tc,TN} < T < 250K at all compositions. From 55Mn NMR spectroscopy, such a response is unambiguously assigned to the intergrowth of a ferromagnetic pseudocubic phase (La(1-z)Pr(z))(1-x)Sr(x)MnO3, with an overall volume fraction estimated as 0.5-0.7% from magnetometry. Evidence is provided for the coupling of the magnetic moments of these inclusions with the magnetic moments of the surrounding (La(1-z)Pr(z))1.2Sr1.8Mn2O7 phase, as in the case of finely dispersed impurities. We argue that the ubiquitous intergrowth phase may play a role in the marked first-order character of the magnetic transition and the metamagnetic properties above Tc reported for double-layer manganites.Comment: 11 pages, 9 figures. Submitted to Phys. Rev.

Effect of pressure on steplike magnetostriction of single crystalline (La0.4_{0.4}Pr0.6_{0.6})1.2_{1.2}Sr1.8_{1.8}Mn2_{2}O7_{7} bilayered manganite

e report the effect of pressure on the steplike magnetostriction of single crystalline bilayered manganite (LaPr)1.2Sr1.8Mn2O8, for our understandings of the ultrasharp nature of the field-induced first-order transition from a paramagnetic insulator to a ferromagnetic metal phase. The application of pressure suppresses a steplike transformation and causes a broad change in the magnetostriction. The injection of an electric current to the crystal also weakens the steplike variation in both the magnetostriction and magnetoresistance. The stabilization of ferromagnetic interaction or the delocalization of charge carriers is promoted with the applied pressure or applied current, resulting in the suppressed steplike behavior. Our findings suggest that the step phenomenon is closely related to the existence of localized carriers such as the short-range charge-orbital ordered clusters.Comment: 5 pages,4 figure