Unusual magnetic properties of NiO nanoparticles embedded in a silica matrix

We have observed unusual magnetic properties of NiO (nickel oxide) nanoparticles embedded in a silica matrix. The sample was synthesized by a method based on the contribution of sol-gel and combustion processes. X-ray powder diffraction (XRPD) of the sample shows the formation of the nanocrystalline NiO phase whereas transmission electron microscope (TEM) reveals spherical-shaped nanoparticles of about 4 nm diameter. Moreover, HRTEM images show lattice fringes of the nanoparticles and defects in the crystal structure. The temperature and field dependence of the magnetization are also measured. The zero-field-cooled (ZFC) measurements show two maximums, one sharp and narrow at low temperatures ∼6.5 K and an other broad one at higher temperature ∼64 K. The FC magnetization shows a continuous increase upon lowering the temperature. The M(H) measurements reveal that NiO nanoparticles display anomalous hysteretic behaviors at low temperatures (below the low temperature maximum in the ZFC curve, 2 K and 5 K) showing that the magnetization initial curve lies below the hysteresis loop for a certain field range. Moreover, jump of the magnetization at low temperatures (2 K and 5 K) are also observed. These features represent novel magnetic properties for nanosized NiO which may be attributed to the surface spins. Moreover, these results indicate that the NiO nanoparticle consists of magnetically disorder shell and antiferromagnetically order core with an uncompensated magnetic moment.     

Synthesis and magnetic properties of nickel nanoparticles deposited on the silicon nanowires

Nickel (Ni) nanoparticles with sizes of ∼35 nm were deposited on the surface of silicon nanowires (SiNWs) by electroless plating technique. The magnetic properties of Ni/SiNWs were investigated. The blocking temperature (T_B) of 370 K was obtained and confirmed by field-cooled (FC) and zero-field-cooled (ZFC) plots. The M-H hysteresis loops from 5 K to 400 K were measured. The saturation magnetization value was ∼4.5 emu/g and the coercivity was ∼375.3 Oe for the loop at 5 K, respectively. While for the loop at 400 K, these values were of ∼2.6 emu/g and ∼33.3 Oe, respectively. The temperature dependence of coercivity followed by the relation H_C(T) = H_C0[1 − (T/T_B)^1/2], indicating a superparamagnetic behavior. The magnetization of superparamagnetic grains in a magnetic field H was better described by Langevin function at 400 K. These novel magnetic properties of Ni/SiNWs were possibly attributed to the paramagnetic defects on the surface of SiNWs.     

Crystallization and magnetic behavior of nanosized nickel ferrite prepared by citrate precursor method

NiFe₂O₄ nanoparticles have been synthesized by citrate precursor gel formation with subsequent heat treatment. Differential thermal and thermogravimetric (DTA/TG) analyses show that the metal citrates decomposed around 230 °C followed by crystallization of the ferrite. X-ray diffraction (XRD) patterns reveal the formation of the cubic spinel phase in the samples after sintering the gel at 350 °C, 500 °C and 700 °C. For the samples annealed at 350 °C and 500 °C a small amount of α-Fe₂O₃ was detected whereas single phase was obtained for the sample annealed at 700 °C. The lattice constant a for all the samples is comparable to the value of the bulk material. The mean crystallite size D_XRD of the samples determined from XRD line broadening is 26.2-28.5 nm. Transmission electron microscope (TEM) analysis shows that the single-phase particles form clusters with the particle size in the range of 21-82.5 nm and the most probable value D_TEM of 55.4 nm. Magnetic measurements show that its Curie temperature T_C is close to the bulk value while the spontaneous magnetization M_s at 5 K is lower than that of the bulk. The thermal variation of M_s in the temperature range from 5 to 300 K can be best fitted to a modified Bloch T^α law with the exponent value α ≈ 2. The magnetization data are explained with reference to the disordered surface spins and the finite size effects. In this investigated temperature range, the coercive force H_c decreases linearly with increasing temperature. The coercivity mechanism in the nanoparticle sample with broad particle size distribution is expected to be complex and different factors which affect the H_c value were proposed.     

Structure, magnetic, and magnetocaloric properties of amorphous and crystalline La0.4Ca0.6MnO3+δ nanoparticles

We report a systematic study of the effects of size reduction on the magnetic and magnetocaloric properties of amorphous and crystalline La_0.4Ca_0.6MnO_3+δ nanoparticles. The materials were synthesized using a modified wet chemical Pechini route, starting with nitrate precursors to produce the perovskite structure. Phase purity, structure, size, and crystallinity were investigated using XRD and TEM. Thermal treatments resulted in nanocrystals with average diameters of 25 nm, 50 nm, and 130 nm, as well as amorphous particles ∼10 nm in diameter. Magnetic measurements revealed broad, second order ferromagnetic transitions in the nanocrystals. As particle size increased from 10 nm to 130 nm, the Curie temperature shifted from 40 K to 255 K. Magnetization, magnetic entropy change (ΔS_M), and refrigerant capacity (RC) also increased with size in the nanocrystalline samples. For a field change of 5 T, the 130 nm particles exhibit a magnetic entropy change of 2.8 J/kg K and a large refrigerant capacity of ∼240 J/kg at 250 K. Interestingly, the 10 nm amorphous particles undergo the sharpest magnetic transition, leading to a larger value of ΔS_M than in the 25 nm or 50 nm crystalline particles. These results reveal that size reduction has a significant impact on the magnetic and magnetocaloric properties of La_0.4Ca_0.6MnO_3+δ.     

Ferromagnetism in ZnTe:Cr film grown on Si(1 0 0)

Zn_1−xCr_xTe (x = 0.0 and 0.05) films were grown on Si(1 0 0) substrate by using thermal evaporation method. The structure of the films was investigated by X-ray diffraction and it showed the formation of ZnCrTe phase with an amorphous background, which indicated poor crystallinity. Composition analysis by XPS disclosed the presence of antiferromagnetic Cr₂O₃ and Cr precipitates. Magnetic domains were observed by using magnetic force microscopy at ambient temperature and the result showed anisotropic domains with an average size of 3.5 nm. Magnetic field dependence of magnetic moment measurements showed obvious hysteresis loop with a coercive field of 121 Oe at 300 K. Temperature dependence of magnetic moment showed short-range ferromagnetic order. The Curie temperature was estimated to be 354.5 K.     

Pyroelectric and electrocaloric effect of 〈1 1 1〉-oriented 0.9PMN-0.1PT single crystal

In this paper, the polarization vs. electric field hysteresis loops of 〈1 1 1〉-oriented 0.9PbMg_1/3Nb_2/3O₃-0.1PbTiO₃ (0.9PMN-0.1PT) single crystal at different temperatures (20-110 °C) were measured. The adiabatic temperature change ΔT of 〈1 1 1〉-oriented 0.9PMN-0.1PT single crystal due to the application or withdraw of electric field were calculated through the thermodynamic relation. The largest temperature change ΔT achieves ∼1 K with only a change of 40 kV/cm electric field, the mechanism of the electrocaloric effect (ECE) is discussed for 0.9PMN-0.1PT crystal. The pyroelectric coefficient of 0.9PMN-0.1PT under bias field was calculated according to the data of hysteresis loop. The result shows that 0.9PMN-0.1PT have large pyroelectric coefficient under bias field, the largest (∂P/∂T)_E value achieves −0.5 μC/cm² K.     

Comparative kinetic and structural analyses of nanocrystalline WC powder synthesis from pre-reduced W under pure and diluted CH4 atmospheres

W nanoparticles derived from WO₃ during heating in H₂ were carburized at 900-1100 K in pure, Ar and H₂-diluted CH₄ atmospheres. It was aimed to elucidate carburization behavior of pre-reduced W powders under various atmospheres and to establish optimal conditions for the synthesis of nanocrystalline WC. Weight measurements, XRD and SEM were used to characterize the products at various stages of the reaction. At 900 K, carburization was limited to the formation of W₂C owing to slow C diffusion. At 1000 K, WC particles were obtained within ~ 75 min using the diluted gas mixtures, while under pure CH₄ atmosphere carburization reaction practically stopped due to pyrolytic carbon skin formed on particle surfaces where C supply was more than consumed. WC powders with particle size 40-65 nm and grain size 15-25 nm were synthesized at 1100 K in a short time under the gas atmospheres studied.     

Structural, magnetic and Mössbauer spectral studies of nanocrystalline Ni0.5Zn0.5Fe2O4 ferrite powders

Nanocrystalline Ni_0.5Zn_0.5Fe₂O₄ powders, synthesized by a combustion method are investigated by X-ray diffraction, vibrating sample magnetometry and Mössbauer spectroscopic techniques. We adopt a strategy to systematically control the particle sizes between 4 and 45 nm simply by changing the elemental stoichiometric coefficient, Φ_e, of the combustion mixture. Curie temperature of the superparamagnetic particles of size 4 nm is higher than that of the bulk particles. Interestingly, bigger particles (45 nm) show a comparable room temperature saturation magnetization and exceptionally very high Curie temperature of 833 K, when compared to that of the bulk Ni_0.5Zn_0.5Fe₂O₄ material (563 K).     

Enhanced exchange bias of isolated Co/CoO nanocaps

We demonstrated the fabrication of the isolated magnetic Co/CoO nanocap array by oxidating the single Co layer which was deposited onto the two dimensional polystyrene sphere array. Compared to the continuous film and thicker nanocap structure, H_E and H_C of the 15 nm Co/CoO isolated cap array were enhanced significantly and were about 4 times as those of the corresponding continuous film, which was ascribed to the formation of the isolated magnetic single domain state due to the magnetic limit around the cap brim after the oxidation treatment. When the beads of the different sizes were used as the substrate, H_E increased when the bead size decreased, which was ascribed to the increase of the localized uncompensated CoO spins.     

Dielectric relaxation, conductivity behaviour and magnetic properties of Mg substituted Ni-Li ferrites

The dielectric properties of Mg substituted Ni-Li spinel ferrites synthesized by sol-gel auto combustion process have been studied using impedance measurements in the frequency range from 10 Hz to 10 MHz and in the temperature range from 310 K to 473 K. The effect of frequency, temperature and composition on dielectric constant (?′), dielectric loss (tan δ) and conductivity (σ) has been discussed in terms of hopping of charge carriers between Fe²⁺ and Fe³⁺ ions. The electrical modulus formulism has been employed to study the relaxation dynamics of charge carriers and the results indicate the presence of non-Debye type of relaxation in the present ferrites. Similar values of activation energies for dc conduction (E_dc) and for conductivity relaxation (E_M″) reveal that the mechanisms of electrical conduction and dielectric polarization are same in these ferrites. A single ‘master curve’ for normalized plots of all the modulus isotherms observed for a given composition indicates the temperature independence of dynamical process for charge carriers. The saturation magnetization and coercivity have been calculated from the hysteresis loop measurements and show striking dependence on the composition.     

Structural investigations of oxidative behavior on nanocrystalline nickel

We have reported a comprehensive study of the structural, magnetic and electrical properties of Ni (core)/NiO (shell) particles, synthesized by control oxidation of ball milled nanocrystalline (nc-) Ni particles in air. A reaction of Ni + (1/2)O₂ → NiO is suspected to occur in the oxidation reaction at the temperature range of 300-800 °C. The phases of the Ni/NiO particles are composed of fcc-Ni and fcc-NiO. The phase compositions of the Ni/NiO particles change with annealing temperature. The Ni/NiO particles have a core-shell monomorphic flower-like microstructure with an average diameter of 20-80 nm. The size reduction and oxidation of the nc-Ni particles leads to a change in microstructure and thermal stability compared to bulk Ni. Thermogravimetric and differential scanning calorimetery analysis are applied to determine the thermal behavior of composites. The initial oxidation of nc-Ni particles is observed to occur around 325 °C (near Curie temperature). Anomalous magnetic and electric behavior is observed at room temperature for the nc-Ni and Ni/NiO particles.     

Enhanced magnetoelectric properties in Bi0.95Ho0.05FeO3 polycrystalline ceramics

Polycrystalline samples of Ho doped BiFeO₃ were prepared by solid state reaction method and effect of partial substitution of Ho on dielectric, magnetic and ferroelectric properties was studied. High temperature dielectric results show two dielectric anomalies both in ? and tan δ, out of which, anomaly at higher temperature (∼400 °C) could be ascribed to antiferromagnetic Néel temperature which, is a signature of magnetoelectric coupling. The magnetic moment is greatly improved and the maximum magnetization was found to be 0.736 emu/g. Saturated ferroelectric hysteresis loops were observed for Bi_0.95Ho_0.05FeO₃ with remnant polarization (P_r) = 1.59 μC/cm², maximum polarization (P_max) = 2.56 μC/cm² and coercivity (E_c) = 5.45 kV/cm. We have conducted comprehensive magnetoelectric and magnetodielectric properties at room temperature. Magnetic field induced ferroelectric hysteresis loop observed in Bi_0.95Ho_0.05FeO₃ is of prime importance.     

Structural and magnetic properties of sputter deposited cobalt-silica nanocomposite thin films

The present study was focused to investigate the effect of Co concentration on structural and, magnetic properties of Co-SiO₂ nanocomposite thin films. Co-SiO₂ nanocomposite films with different cobalt atomic concentration up to 49 at% were synthesized using direct current (DC) and radiofrequency (RF) magnetron co-sputtering. TEM and XRD analyses reveal the formation of both FCC (1 1 1) and HCP (1 0 1) phases in all the samples. The particle size and surface roughness of these films is found to increase with increase in cobalt concentration. Magnetic measurements reveal that the embedded cobalt nanoparticles behave as superparamagnets when their size is ≤16 nm. The coercivity at 3 K decreases while value of blocking temperature increases with increase in the size of embedded Co nanoparticles.     

Phase, structural, and magnetocaloric properties of high temperature annealed LaFe11.6Si1.4BX

The phase relation, microstructural, hysteresis, Curie temperature, and magnetocaloric effects of LaFe_11.6Si_1.4B_x (x = 0.1, 0.2, 0.3, 0.4, and 0.5) prepared by arc-melting and then annealed at 1373 K (1.5 h) + 1523 K (5 h) were investigated. It was found that the main phase is NaZn₁₃-type phase, the impurity phases include α-Fe, Fe₂B, and small amount of La₅Si₃. The boron atom can dissolve into the crystal lattice of LaFe_11.6Si_1.4B_x to form interstitial solid solution, but the content of solid solution is not up to x = 0.5. For LaFe_11.6Si_1.4B_x (x = 0.1, 0.3, and 0.5) compounds, the Curie temperature T_C increases from 190.6 to 198.3 K with the increasing of B content from x = 0.1 to 0.5. The first order magnetic transition behavior becomes weaker and magnetic entropy change ΔS_M (T, H) drops with the increasing of B content, respectively. However, ΔS_M (T, H) still remains a large value, 11.18 J/kg K, when x reaches to 0.5 at 0-2 T. An attractive feature is that both thermal and magnetic hysteresis can be reduced remarkably by introducing B. The maximum magnetic hysteresis loss near T_C drops from 22.52 to 4.95 J/kg when the content of B increases from x = 0.1 to 0.5.     

Magnetic properties of mechanochemically synthesized γ-Fe2O3 nanoparticles

The synthesis of mono-dispersed γ-Fe₂O₃ nanoparticles by mechanochemical processing was demonstrated for the first time, via the solid-state exchange reaction Fe₂(SO₄)₃ + 3Na₂CO₃ → Fe₂(CO₃)₃ + 3Na₂SO₄ → Fe₂O₃ + 3Na₂SO₄ + 3CO₂(g) and subsequent heat treatment at 673 K. The nanoparticles had a volume-weighted mean diameter of 6 nm and a narrow size distribution with the standard deviation of 3 nm. The particles showed a superparamagnetic nature with the superparamagnetic blocking temperature of 56.6 K. The anisotropy constant was 6.0 × 10⁶ erg/cm³, two orders of magnitude larger than the magnetocrystalline anisotropy constant of bulk γ-Fe₂O₃. The detailed analysis of the magnetic properties indicated that the γ-Fe₂O₃ nanoparticles had a core-shell structure, consisting of a ferrimagnetic core of ∼4 nm in diameter having a collinear spin configuration and a magnetically disordered shell of ∼1.2 nm in thickness.     

Comparison of electrical characteristics for p-type and n-type organic thin film transistors using copper phthalocyanine

The p-type and n-type organic thin film transistors (OTFTs) were fabricated in the same experimental conditions by using hexadecahydro copper phthalocyanine (H₁₆CuPc) and hexadecafluoro copper phthalocynine (F₁₆CuPc) molecules, respectively. The mobilities of H₁₆CuPc and F₁₆CuPc-based OTFT devices in saturation region were measured to be ∼1.22 × 10⁻³ cm²/V s and ∼1.04 × 10⁻³ cm²/V s, respectively. The temperature dependence of the mobility and activation energy (E_a) for both OTFTs were measured in saturation and linear regions of the drain-source current. We found that the E_a of the F₁₆CuPc-based OTFTs was lower than that of H₁₆CuPc-based ones. The gate voltage (V_g) dependence of the field-effect mobility measured in linear region for the F₁₆CuPc-based OTFTs was more stable, i.e., weaker variation of the field-effect mobility with increasing V_g, than that of the H₁₆CuPc-based ones. The high electron affinity of the hexadecafluorine (F₁₆) in CuPc contributed to the effective electron accumulation in the active channel.     

Enhanced magnetization and magnetoelectric coupling in hydrogen treated hexagonal YMnO3

The single phase hexagonal YMnO₃ has been synthesized via sol-gel route by adopting two different sintering conditions. In one case, sintering has been done at ∼700 °C in Ar/H₂ atmosphere and in other case it has been done at ∼1250 °C in air. Magnetic measurements of the samples, synthesized by sintering at relatively lower temperature in Ar/H₂ atmosphere, show the enhanced ferromagnetic behaviour at 10 K. M-H curve shows that the value of saturation magnetization (M_s) at 10 K is 8.04 emu/g for Ar/H₂ sintered sample while it is 2.93 emu/g for the air sintered sample. Moreover, a weak ferromagnetic signal at room temperature has been observed in YMnO₃ compound. Magnetization versus magnetic field (M-H) curves of hydrogen treated samples, measured at room temperature, show small kink in the linear variation near origin, possibly due to presence of weak ferromagnetic interactions in the samples at room temperature. However, the polarization-electric field (P-E) curve shows weak ferroelectric characteristics for the Ar/H₂ sintered samples. It is suggested that the enhanced ferromagnetism in Ar/H₂ sintered sample originates from the presence of oxygen vacancies in the Ar/H₂ sintered samples. Moreover, the magnetoelectric coupling coefficient at room temperature is improved to 106 mV/cm Oe for Ar/H₂ sintered sample as compared to 96 mV/cm Oe for air sintered sample at 40 kHz ac magnetic field frequency.     

Microstructure and optical absorption properties of Au-dispersed CoO thin films

Au nanoparticles dispersed cobalt monoxide (CoO) composite films were fabricated via a chemical solution approach combined with a spin-coating processing. Au particles were spherical approximately and uniformly dispersed in the amorphous CoO matrix. The mean diameters of Au particles in the Au/CoO thin films with 40 mol% Au are about 30 nm. The optical absorption peaks due to the surface plasmon resonance (SPR) of Au particles were observed in the UV-vis absorption spectra in the wavelength range of 550-650 nm. The SPR peaks exhibit a red shift and intensify with increasing Au content from 10 to 40 mol%, but show a blue shift and weaken from 40 to 60 mol%. The band gap E_g decreases with increasing Au contents from 10 to 40 mol% but increases by further increasing Au content.     

Exchange biasing in SFMO/SFWO double perovskite multilayer thin films

In the present study, we have studied the exchange bias interaction in ferromagnetic Sr₂FeMoO₆ (SFMO)/antiferromagnetic Sr₂FeWO₆ (SFWO) multilayer thin films deposited on single crystal LaAlO₃ substrates using KrF pulsed laser deposition technique. XRD pattern revealed that SFMO, SFWO and their multilayer thin films were highly oriented along the c-axis. The microstructure studied by atomic force microscopy was found to be uniform, fine, dense and homogenous in nature. The observed magnetization-temperature curves showed Neel temperature T_N ∼ 37 K for SFWO and Curie temperature T_C > 320 K for SFMO thin films. For multilayer, the field cooled magnetization-field curve was shifted horizontally and the direction of the horizontal shift is opposite to that of H_FC, indicating an exchange bias effect. Exchange bias field H_E was found to decrease with increase in temperature and approached to zero at blocking temperature.     

Magnetic properties of the 1/1 approximant Ag42In42Gd16 to the icosahedral quasicrystal Ag-In-Gd

The structural, magnetic, and ¹⁵⁵Gd Mössbauer spectral properties of the 1/1 approximant Ag₄₂In₄₂Gd₁₆ to an icosahedral quasicrystal Ag-In-Gd are reported. Based on dc magnetic susceptibility measurements, it is shown that the studied compound develops no long-range magnetic order in the temperature range 1.8-300 K. The dc zero-field-cooled and field-cooled susceptibility data indicate that the 1/1 approximant Ag₄₂In₄₂Gd₁₆ is a spin glasss with freezing temperature T_f = 3.6(1) K. This is further confirmed by the analysis of the frequency dependence of T_f using the Vogel-Fulcher law and the dynamic scaling behavior near T_f. It is argued that the spin freezing process is a true equilibrium phase transition rather than a nonequilibrium phenomenon. The large frustration parameter of the studied compound indicates that it belongs to a category of strongly geometrically frustrated magnets. The ¹⁵⁵Gd Mössbauer spectra of the 1/1 approximant Ag₄₂In₄₂Gd₁₆ confirm that the Gd spins are frozen at 1.5 K and are fluctuating at 4.6 K. The Debye temperature of the 1/1 approximant Ag₄₂In₄₂Gd₁₆ is 200(1) K.