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 d 0 systems and other defective oxides that contain no magnetic ions. Here, we investigate TiO 2 (rutile) containing 1 -5% of iron cations and find that the roomtemperature 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 Fe 2+ and Fe 3+ ions in the oxide lattice. The phase diagram for the model shows how inhomogeneous Stoner ferromagnetism depends on the total number of electrons N tot , 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.
Thin films of SnO 2 prepared by pulsed-laser deposition on R-cut sapphire substrates exhibit ferromagnetic properties at room temperature when they are doped with Cr, Mn, Fe, Co, or Ni, but not with other 3d cations. Extrapolated Curie temperatures are generally in excess of 500 K. The moment of the films is roughly independent of doping level, from 0.1-15 at. %, with a value per unit substrate area of 200± 100 B nm −2 . When magnetization is expressed as a moment per 3d dopant ion, it varies from more than the spin-only value at low concentrations to less than 0.2 B /ion near the percolation threshold. Greatest values are found for iron. The magnetization of the films is highly anisotropic with values when the field is applied perpendicular to the substrate more than double the in-plane values. There is little hysteresis except at high doping levels. The oxides are degenerate n-type semiconductors with a Hall mobility of 100 cm 2 V −1 s −1 and 1.4ϫ 10 19 carriers cm −3 in a one-band model, but no anomalous Hall effect or magnetoresistance was observed at room temperature. The data are discussed in relation to ͑a͒ the donor impurity-band model of ferromagnetism in semiconductors and ͑b͒ the magnetic defect model.
Spontaneous supercrystal organisation of semiconductor nanorods (CdS and CdSe) of different aspect ratios into ordered superstructures was obtained by controlled evaporation of a nanorod solution. The rods either align into two dimensional close packed perpendicular arrays or into one dimensional rail tracks depending on the total interaction energy between the rods in solution. A detailed study has 10 identified critical factors that affect this interaction energy such as nanorod concentration, surface charge, dipole moment and solvent nature (polarity and volatility), thereby allowing a general approach to control the nature of nanorod assembly (1D or 2D). Molecular dynamics (MD) of small charged nanorods showed that opposite dipolar alignment (antiferromagnetic) was the preferred rod orientation during selfassembly.15
Here, we present an optical probe to determine the pore-filling fraction of the hole-conductor 2,2-7,7-tetrakis-N,N-di-pmethoxyphenylamine-9,9-spirobifluorene (spiro-OMeTAD) into mesoporous photoanodes in solid-state dye-sensitized solar cells (ss-DSCs). Based on refractive index determination by the film's reflectance spectra, and using effective medium approximations, we can extract the volume fractions of the constituent materials and hence quantify pore-filling. This non-destructive method can be used with complete films and does not require detailed model assumptions.pore-filling fractions of up to 80% were estimated for optimized solid-state DSC photoanodes, which is higher than that previously estimated by indirect methods.Additionally, we have determined transport and recombination lifetimes as a function of the pore-filling fraction via photovoltage and photocurrent decay measurements. While extended electron lifetimes were observed with increasing pore-filling fractions, no trend was found in the transport kinetics. The data suggests that a pore-filling fraction of at least 60% is necessary to achieve optimized performance in ss-DSCs. This degree of pore-filling is even achieved in 5 µm thick mesoporous photoanodes. We can therefore conclude from this study that pore-filling is not a limiting factor in the fabrication of thick ss-DSCs.
Spontaneous elongation from nanorod to nanowire in the presence of an amine is reported for nanocrystals of cadmium sulfide and silver sulfide (cation exchanged from CdS). Elongation occurs instantaneously where the final aspect ratio is a controllable multiple of the original nanorod length.Transmission electron microscopy (TEM) data and kinetic modeling reveal the influential factors on the attachment process are the concentration of amine, duration and temperature of the reaction. The elongated nanorods are further characterized by X-Ray diffraction (XRD), photoluminescence (PL), ultraviolet-visible spectroscopy (UV-Vis) and X-ray photoelectron spectroscopy (XPS). A mechanism of oriented attachment is evidenced by the doubling in length of asymmetrically gold tipped CdS nanorods with the corresponding absence of elongation in symmetrically tipped nanorods.1
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