Organic-inorganic perovskites are a class of solution-processed semiconductors holding promise for the realization of low-cost efficient solar cells and on-chip lasers. Despite the recent attention they have attracted, fundamental aspects of the photophysics underlying device operation still remain elusive. Here we use photoluminescence and transmission spectroscopy to show that photoexcitations give rise to a conducting plasma of unbound but Coulomb-correlated electron-hole pairs at all excitations of interest for light-energy conversion and stimulated optical amplification. The conductive nature of the photoexcited plasma has crucial consequences for perovskite-based devices: in solar cells, it ensures efficient charge separation and ambipolar transport while, concerning lasing, it provides a low threshold for light amplification and justifies a favourable outlook for the demonstration of an electrically driven laser. We find a significant trap density, whose cross-section for carrier capture is however low, yielding a minor impact on device performance.
The structure and the magnetic properties of a series of Fe 2 O 3 -SiO 2 nanocomposites (9-33 wt % Fe 2 O 3 ), prepared by a sol-gel method and submitted to thermal treatments in the temperature range 300-900 °C, were investigated through XRD, TEM, EPR, and magnetic susceptibility measurements. Superparamagnetic iron(III) oxide nanoparticles with a narrow size distribution, dispersed over the amorphous silica matrix, are present in all the samples. They are mostly amorphous, antiferromagnetic in the samples treated at low temperatures. At T > 700 °C, a lot of γ-Fe 2 O 3 crystalline ferrimagnetic nanoparticles (4-6 nm) are formed, while a further increase of the temperature results in the γto R-Fe 2 O 3 transformation. The variation of iron oxide content affects the abundance of γ-Fe 2 O 3 formation, which reaches the maximum percent values in the more dilute samples. In the more concentrated samples, while the amount of maghemite is still growing, antiferromagnetic R-Fe 2 O 3 begins to form. As a consequence, the saturation magnetization lowers in the samples with higher Fe 2 O 3 content. Also, interparticle interactions, evidenced by fitting susceptibility values versus temperature and by EPR observations, contribute to such a decrease.
The magnetic properties of cobalt ferrite nanoparticles dispersed in a silica matrix in samples with different concentrations (5 and 10 wt% CoFe2O 4) and same particle size (3 nm) were studied by magnetization, DC and AC susceptibility, and Mossbauer spectroscopy measurements. The results indicate that the particles are very weakly interacting. The magnetic properties (saturation magnetization, anisotropy constant, and spin-canting) are discussed in relation to the cation distribution.
The possibility to finely control nanostructured cubic ferrites (M(II)Fe2O4) paves the way to design materials with the desired magnetic properties for specific applications. However, the strict and complex interrelation among the chemical composition, size, polydispersity, shape and surface coating renders their correlation with the magnetic properties not trivial to predict. In this context, this work aims to discuss the magnetic properties and the heating abilities of Zn-substituted cobalt ferrite nanoparticles with different zinc contents (ZnxCo1-xFe2O4 with 0 < x < 0.6), specifically prepared with similar particle sizes (∼7 nm) and size distributions having the crystallite size (∼6 nm) and capping agent amount of 15%. All samples have high saturation magnetisation (Ms) values at 5 K (>100 emu g(-1)). The increase in the zinc content up to x = 0.46 in the structure has resulted in an increase of the saturation magnetisation (Ms) at 5 K. High Ms values have also been revealed at room temperature (∼90 emu g(-1)) for both CoFe2O4 and Zn0.30Co0.70Fe2O4 samples and their heating ability has been tested. Despite a similar saturation magnetisation, the specific absorption rate value for the cobalt ferrite is three times higher than the Zn-substituted one. DC magnetometry results were not sufficient to justify these data, the experimental conditions of SAR and static measurements being quite different. The synergic combination of DC with AC magnetometry and (57)Fe Mössbauer spectroscopy represents a powerful tool to get new insights into the design of suitable heat mediators for magnetic fluid hyperthermia.
Molecular coating of nanoparticles represents probably the most important and, at the same time, critical step to design new nanostructured magnetic materials. The interaction between molecules and surface atoms leads to a strong modification of surface magnetic properties, that are one of the key points in the physics of magnetic nanoparticles. In this paper the magnetic properties of CoFe2O4 nanoparticles (⟨D⟩ ≅ 4–8 nm) coated with oleic acid have been investigated in order to clarify the role of the molecular coating on the interparticle interactions and surface anisotropy. An increase of magnetic anisotropy (i.e., coercive field and anisotropy constant) with particle size is observed in coated nanoparticles, indicating that the magnetic anisotropy is governed mainly by its magneto-crystalline component. The removal of molecular coating induces a strong increase of anisotropy, because of the increase of its surface component, as indicated by the increase of exchange bias field.
The magnetic properties of ultra-small (3 nm) CoFe(2)O(4) nanoparticles have been investigated by DC magnetization measurements as a function of temperature and magnetic field. The main features of the magnetic behaviour are blocking of non-interacting particle moments (zero-field-cooled magnetization T(max) approximately 40 K), a rapid increase of saturation magnetization (up to values higher than for the bulk material) at low T and an increase in anisotropy below 30 K due to the appearance of exchange bias. The low temperature behaviour is determined by a random freezing of surface spins. Localized spin-canting and cation distribution between the two sublattices of the spinel structure account quantitatively for the observed increase in saturation magnetization.
The magnetic properties of cobalt ferrite-silica nanocomposites with different concentrations (15, 30, and 50 wt %) and sizes (7, 16, and 28 nm) of ferrite particles have been studied by static magnetization measurements and Mossbauer spectroscopy. The results indicate a superparamagnetic behavior of the nanoparticles, with weak interactions slightly increasing with the cobalt ferrite content and with the particle size. From high-field Mossbauer spectra at low temperatures, the cationic distribution and the degree of spin canting have been estimated and both parameters are only slightly dependent on the particle size. The magnetic anisotropy constant increases with decreasing particle size, but in contrast to many other systems, the cobalt ferrite nanoparticles are found to have an anisotropy constant that is smaller than the bulk value. This can be explained by the distribution of the cations. The weak dependence of spin canting degree on particle size indicates that the spin canting is not simply a surface phenomenon but also occurs in the interiors of the particles.
CoFe(2)O(4) nanoparticles (
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