Physics

Cupric oxide nanoparticles of ∼8–10 nm width and 40–45 nm length self assembled as large particles ∼1–1.5 μm have been investigated, in the 10–325 K temperature range, using magnetic and dielectric measurements. In magnetic measurements a single broad peak at ∼230 K in a zero field cooled sample has been observed. Coercivity, in magnetization measurements at 10 K, suggests that the nanoparticles are core-shell type particles with an antiferromagnetic core and a ferromagnetic shell. Dielectric measurements, at various frequencies from 3.7 Hz to 949 kHz, exhibit a sharp peak at 284 K followed by weak anomalies around 213 and 230 K.

We report the temperature-dependent Raman and dielectric spectroscopy of chemically synthesized BiFeO3 nanoparticles (average size 50−60 nm). The Raman spectra (90−700 K) show two sets of transitions in the lowest Raman E mode, associated with Bi−O bond motion situated in close proximity to the spin reorientation transitions reported for BiFeO3, thereby indicating the existence of possible coupling between magnons and phonons for particle size below the helical order parameter (62 nm). These transitions are slightly shifted in temperature in comparison to the bulk single crystals. We also observe a step-like behavior in Raman peak position around the Neel temperature, suggesting that the phonons are influenced by the magnetic ordering in nanosized BiFeO3. The heat-flow measurements show two sharp endothermic peaks at 1094 and 1223 K representing rhombohedral to orthorhombic or monoclinic transition followed by transition into the cubic phase above 1200 K. The low temperature (20−325 K), frequency-dependent (1−106 Hz) dielectric constant and loss tangent measurements show that the loss tangent (10−3) and ac conductivity values (10−8 Ohm−1-cm−1) are orders of magnitude lower than the reported values for BiFeO3 ceramics, indicating high levels of ionic purity of our samples. The real part of the permittivity shows a slight reduction in its value (30) in comparison to the bulk single crystals. Similar to the Stokes Raman shift, its temperature-dependent dielectric constant also shows four weak anomalies at 85, 168, 205, and 230 K situated in close proximity to the spin reorientation transitions, indicating magnetoelectric coupling.

The rare earth orthochromites are extremely interesting due to the richness of their optical, dielectric, and magnetic properties as well as due to their multiferroic properties which make them suitable materials to study in the nanoregime. However, the wet-chemical synthesis of these materials in nanosize is nontrivial. Here, we report for the first time, the detailed Raman spectra as well as magnetic and dielectric properties of chemically synthesized GdCrO3 nanoparticles of size ranging from 40 to 60 nm. The magnetic properties are dictated by competing Cr3+–Cr3+, Gd3+–Cr3+, and Gd3+–Gd3+ superexchange interactions in different temperature regions, resulting into an antiferromagnetic ordering at 167 K due to the Cr3+–Cr3+ followed by weak ferromagnetic ordering due to the onset of Cr3+–Gd3+ interactions. At lower temperature, it shows weak antiferromagnetic ordering due to Gd3+–Gd3+ interaction. Below 95 K, GdCrO3 nanoparticles showed the presence of negative magnetization due to Gd3+ and Cr3+ interactions resulting into weak ferromagnetic coupling. The Raman spectroscopy shows the characteristic Raman shifts indicating that below 450 cm−1, Gd3+ ions play a dominant role in determining the phonon frequencies of GdCrO3, and above 450 cm−1, the Cr+3 ions dominate. We also present for the first time the low temperature dielectric constant and loss tangent data for GdCrO3 in a broad temperature and frequency range. The dielectric constant shows a decrease in comparison to the bulk values due to the size dependent effects. It also shows a peak centered at around 320 K above which it shows a sharp decrease. The dielectric loss value in GdCrO3 nanoparticles is quite small and shows an interesting frequency dependent anomaly at lower temperature which might be due to the coupling between magnetic and dielectric order parameters.