Subhash Thota

A comparative study of the magnetic properties of bulk and nanocrystalline Co3O4

A comparative study of the magnetic and electron paramagnetic resonance (EPR) parameters of bulk and Co3O4 nanoparticles (NP), synthesized by a sol–gel process, is presented. Both samples possess the cubic phase with a slightly lower (by 0.34%) lattice parameter for the Co3O4 NP. The average crystallite size D = 17 nm determined by x-ray diffraction (XRD) for the Co3O4 NP is quite consistent with the electron microscopic observations. The bulk Co3O4 has particle size in the 1–2 µm range. A Neel temperature of TN = 30 K (lower than the 40 K usually quoted in the literature) is determined from the analysis of the magnetic susceptibility versus temperature data for bulk Co3O4. This TN = 30 K is in excellent agreement with the TN = 29.92 K reported from specific heat measurements. The Co3O4 NP powder exhibits a still lower TN = 26 K, possibly due to the associated finite size effects. The values of coercivity, Hc = 250 Oe, and exchange bias, He = −350 Oe, together with the training effect have been observed in the Co3O4 NP sample (cooled in 20 kOe). Both Hc and He approach zero as . For T>TN, the χ versus T data for both samples fit the modified Curie–Weiss law (χ = χ0+C/(T+θ)). The magnitudes of C, θ and TN are used to determine the following: exchange constants J1ex = 11.7 K, J2ex = 2.3 K, and magnetic moment per Co2+ ion μ = 4.27 μB for bulk Co3O4; and J1ex = 11.5 K, J2ex = 2.3 K and μ = 4.09 μB for Co3O4 NP. EPR yields a single Lorentzian line near g = 2.18 in both samples but with a linewidth ΔH that is larger for the Co3O4 NP. Details of the temperature dependence of ΔH, line intensity I0, and disappearance of the EPR on approach to TN are different for the two samples. These effects are discussed in terms of spin–phonon interaction and additional surface anisotropy present in Co3O4 NP.

Size-dependent shifts of the Néel temperature and optical band-gap in NiO nanoparticles

Bulk NiO is a well-known antiferromagnet with Neel temperature TN(∞) = 524 K and an optical band-gap Eg = 4.3 eV. With decrease in particle size D from 40 nm to 4 nm of NiO, systematic changes of TN and Eg are observed and discussed here. From magnetic measurements, the changes in TN with D are found to fit finite-size scaling equation TN(D) = TN(∞) [1 − (ξo/D)λ] with λ = 3.2 ± 0.5 and ξo = 3.2 ± 0.2 nm, in good agreement with the predictions for a Heisenberg system. The observed blue shifts of Eg with decrease in D reaching Eg = 5.12 eV for D ∼ 4 nm are likely due to quantum confinement and non-stoichiometry.

Magnetic frustration and short-range ordering in cubic defect spinel MgMnO3

Magnetic properties of bulk MgMnO3, a cubic defect spinel with the structure 4MgMnO3=3[Mg2+][Mg+2 1/3Mn4+ 4/3◻1/3]O4, are reported. For T > 150 K, magnetization M vs T data fits the Curie-Weiss law with μ ≃ 4μB expected for Mn4+ and θ ≃ −40 K indicating antiferromagnetic Mn4+-Mn4+coupling. For T < 150 K, a blocking temperature TB ≃ 15 K is observed below which coercivity increases with decreasing T. The electron magnetic resonance spectra yield a single broad line with g ≃ 1.9 whose linewidth increases with decreasing T leading to a peak at TB. As predicted in spinels with magnetic ions only on the B-sites, these observations suggest a magnetically frustrated state with short-range order only.

Synthesis and magnetic properties of nanocrystals of cubic defect spinel MgMnO3

Synthesis and magnetic properties of nanocrystals (size ≃22 nm) of cubic spinel MgMnO3 with the defect structure [Mg2+][Mg1/32+Mn4/34+◻1/3]O4 are reported. Analysis of the magnetization M versus T (2–370 K) and M versus H (up to 65 kOe) data shows a blocking temperature TB≃11 K and an estimated Neel temperature TN∼150 K above which the Weiss temperature θ=−7 K and μ=3.91 μB/Mn4+. For TB<T<TN, fit of the M versus H data to modified Langevin function yields 35 μB as magnetic moment/particle, resulting from the defect structure.

Peculiarities of the temperature dependence of electron spin resonance and Raman studies of Zn1−xNixO/NiO two-phase nanocomposites

A meticulous investigation of electron-spin-resonance (ESR) and Raman spectroscopy of the two-phase nanocomposites of Zn1−xNixO/NiO is reported. The temperature variation of X-band ESR parameters viz., resonance field HR(T) and line-width ΔHPP(T) follows the power-law variation (δHR = (ΔHPP)n) of Nagata and Ishihara model, which was used to understand the orientation of statistical ensemble of particles with respect to a given direction of the anisotropy axis. This analysis yields the exponent “n” ≃ 2.13 and 2.85 for the composite system Zn1−xNixO/NiO and pure NiO suggesting the presence of partial and randomly oriented ellipsoidal nanocrystallites, respectively. The Raikher and Stepanov model has been employed to probe the role of amorphous Ni3+ clusters on the observed ESR spectra. Interestingly, after Ni substitution, a new zone boundary phonon mode was noticed at 129 cm−1 for all the samples, which is usually forbidden in the first-order Raman scattering for wurtzite ZnO. In addition to the 2M magnon ...

Synthesis and Optical Characterization of Mg1-xNixO Nanostructures

An attempt has been made here to synthesize nano-powders via sol-gel process. These powders are shown to possess an f.c.c. (NaCl-type) structure with a typical lattice parameter of  A for when decomposition of dried oxalate gel product is carried out at 600°C for 2 h in air. Moreover, they exhibit (i) clusters/agglomerates of nanosize particles and (ii) high BET specific surface area (123.0–135.5 m2/g). Also, the infrared absorption spectra reveal their strong affinity to water. The UV-Vis absorption peaks appearing at ~202 nm, 296 nm, and 379 nm are associated with oxygen defect centres and correspond to the electronic transitions (i) (, , or ), (ii) (, or ) and (iii) (), respectively. The incorporation of Ni2

Size-dependent structural, magnetic, and optical properties of MnCo2O4 nanocrystallites

Finite-size (d = 5.4–112 nm) and surface effects on the structural, optical, and magnetic properties of ferrimagnetic inverse-spinel MnCo2O4 are reported. For d ≥ 87 nm, partial tetragonal distortion of the inverse spinel-lattice was observed. The Curie temperature TC of MnCo2O4 nanostructures, as determined by dc-magnetic susceptibility (χ) measurements, follows a finite-size scaling relation TC(d) = TC(∞)[1−(ξ0/d)λ] with a shift exponent λ = 0.75 ± 0.15 and microscopic correlation length ξ0 = 1.4 ± 0.3 nm, which is consistent with the mean field theory. For T > TC, χ(T) fits Neels expression for the two-sublattice model with antiferromagnetic molecular field (exchange) constants NBB ∼ 85.16 (JBB ∼ 2.94 × 10−22 J), NAB ∼ 110.96 (JAB ∼ 1.91 × 10−22 J), and NAA ∼ 43.8 (JAA ∼ 1.13 × 10−22 J) and asymptotic Curie temperature Ta ∼ 717.63 K. The optical energy bandgap Eg, evaluated from the Kubelka-Munk function ( [ F ( R ∞ ) ℏ ω ] 2 = C2( ℏ ω - Eg)) is blueshifted to 2.4 eV (d ∼ 5.4 nm) from 1.73 eV (d ∼ 112...

Reentrant spin-glass behavior and bipolar exchange-bias effect in “Sn” substituted cobalt-orthotitanate

We report the co-existence of longitudinal ferrimagnetic behavior with Neel temperature TN ∼ 46.1 K and reentrant transverse spin-glass state at 44.05 K in Tin (Sn) doped cobalt-orthotitanate (Co2TiO4). The ferrimagnetic ordering is resulting from different magnetic moments of Co2+ on the A-sites (3.87 μB) and B-sites (5.069 μB). The magnetic compensation temperature (TCOMP) shifts from 31.74 K to 27.1 K when 40 at. % of “Sn4+” substitutes “Ti4+” at B-sites where the bulk-magnetization of two-sublattices balance each other. For T > TN, the dc-magnetic susceptibility (χdc = M/Hdc) fits well with the Neels expression for the two-sublattice model with antiferromagnetic molecular field constants NBB ∼ 15.44, NAB ∼ 32.01, and NAA ∼ 20.88. The frequency dependence of ac-magnetic susceptibility χac data follows the Vogel-Fulcher law, and the power-law of critical slowing-down with “zν” = 6.01 suggests the existence of spin-clusters (where “z” and “ν” being dynamic critical-exponent and correlation length of cri...

Low-temperature anomalous magnetic behavior of Co2TiO4 and Co2SnO4

We report the low-temperature anomalous magnetic behavior of ferrimagnetic spinels cobalt orthotitanate (Co2TiO4), which exhibits magnetic compensation behavior across 31.74 K, and cobalt orthostannate (Co2SnO4) exhibiting two sequential magnetic transitions, namely (i) ferrimagnetic to paramagnetic transition with Neel temperature TN ∼ 41 K and reentrant spin-glass behavior with glass transition temperature TSG ∼ 39 K. The Arrott plot (H/M versus M2) criterion has been used to extricate the order of sequential magnetic transitions occurring below TN. Negative slopes of the Arrott plots below 32 K, metamagnetic-like character of the M-H isotherms, anomalies in the specific-heat (CP T−1 versus T) below 15 K, and a zero-crossover of isothermal magnetic-entropy-change (ΔS) signify the presence of pseudo first-order discontinuous magnetic phase transition in the low-temperature regime 5 K ≤ T ≤ 32 K. The dc- and ac-susceptibilities of both Co2TiO4 and Co2SnO4 are interpreted in terms of frozen-spin-clusters, ...

Nature of Magnetic Ordering in Cobalt‐Based Spinels

In this chapter, the nature of magnetic ordering in cobalt‐based spinels Co3O4, Co2SnO4, Co2TiO4, and Co2MnO4 is reviewed, and some new results that have not been reported before are presented. A systematic comparative analysis of various results available in the literature is presented with a focus on how occupation of the different cations on the A‐ and B‐sites and their electronic states affect the magnetic properties. This chapter specifically focuses on the issues related to (i) surface and finite‐size effects in pure Co3O4, (ii) magnetic‐compensation effect, (iii) co‐existence of ferrimagnetism and spin‐glass‐like ordering, (iv) giant coercivity (HC) and exchange bias (HEB) below the glassy state, and (v) sign‐reversal behavior of HEB across the ferri/ antiferromagnetic Néel temperature (TN) in Co2TiO4 and Co2SnO4. Finally, some results on the low‐temperature anomalous magnetic behavior of Co2MnO4 spinels are presented.