The structural state and static and dynamic magnetic properties of TbCu2 nanoparticles are reported. The nanoparticles were produced by mechanical milling under inert atmosphere with low milling times ≤ 15 hours. The randomly dispersed nanoparticles as detected by TEM retain the bulk symmetry with an orthorhombic Imma lattice and Tb and Cu in 4c positions. Rietveld refinements confirm that the milling produces a controlled reduction of particle sizes reaching down to ≃ 6 nm and an increase of the microstrain ≃ 0.6 %. The DC-susceptibility shows a reduction of the Néel transition (from 49 K to 43 K) and a progressive increase of the spin glass peak (from 9 to 15 K) in the zero field cooled magnetization with size reduction. The exchange anisotropy is very weak (bias field of ≃ 30 Oe) and is due to the presence of a disordered (thin) shell coupled to the antiferromagnetic core. The dynamic susceptibility evidences a critical slowing down in the spin disordered state with a tendency to increase of zv and β exponents when the size becomes smaller (zv ≃ 6.6 and β ≃ 0.85). A Rietveld analysis of neutron diffraction patterns 1.8 ≤ T ≤ 60 K including the magnetic structure determination reveals that there is a reduction of the expected moment (≃ 80 %) which must be connected to the presence of the disordered particle shell. The core magnetic structure retains the bulk antiferromagnetic arrangement. The overall interpretation is based on a superantiferromagnetic behavior which at low temperatures coexists with a canting of surface moments. We propose a novel magnetic phase diagram as a function of the particle size.
Recently, potential technological interest has been revealed for the production of magnetocaloric alloys using Rare-Earth intermetallics. In this work, three series of TbxR1−xCu2 (R ≡ Gd, La, Y) alloys have been produced in bulk and nanoparticle sizes via arc melting and high energy ball milling. Rietveld refinements of the X-ray and Neutron diffraction patterns indicate that the crystalline structure in all alloys is consistent with TbCu2 orthorhombic Imma bulk crystalline structure. The analyses of the DC-magnetisation (MDC) and AC-susceptibility (χAC) show that three distinct degrees of disorder have been achieved by the combination of both the Tb3+ replacement (dilution) and the nanoscaling. These disordered states are characterised by transitions which are evident to MDC, χAC and specific heat. There exists an evolution from the most ordered Superantiferromagnetic arrangement of the Tb0.5La0.5Cu2 NPs with Néel temperature, TN∼ 27 K, and freezing temperature, Tf∼ 7 K, to the less ordered weakly interacting Superparamagnetism of the Tb0.1Y0.9Cu2 nanoparticles (TN absent, and TB∼ 3 K). The Super Spin Glass Tb0.5Gd0.5Cu2 nanoparticles (TN absent, and Tf∼ 20 K) are considered an intermediate disposition in between those two extremes, according to their enhanced random-bond contribution to frustration.
A series of GdCu 2 nanoparticles with controlled sizes ranging from 7 nm to 40 nm has been produced via high-energy inert-gas ball milling. Rietveld refinements on the X-ray diffraction measurements ensure that the bulk crystalline I m m a structure is retained within the nanoparticles, thanks to the employed low milling times ranging from t = 0.5 to t = 5 h. The analysis of the magnetic measurements shows a crossover from Superantiferromagnetism (SAF) to a Super Spin Glass state as the size decreases at NP size of ⟨ D ⟩ ≈ 18 nm. The microstrain contribution, which is always kept below 1%, together with the increasing surface-to-core ratio of the magnetic moments, trigger the magnetic disorder. Additionally, an extra contribution to the magnetic disorder is revealed within the SAF state, as the oscillating RKKY indirect exchange achieves to couple with the aforementioned contribution that emerges from the size reduction. The combination of both sources of disorder leads to a maximised frustration for ⟨ D ⟩ ≈ 25 nm sized NPs.
An ensemble of superantiferromagnetic NdCu 2 nanoparticles has been produced to perform a detailed analysis of magnetic excitations using inelastic neutron scattering. Neutron diffraction measurements indicate a mean nanoparticle size of D ≈ 13 nm, where the bulk commensurate antiferromagnetic structure is retained at the nanoparticle core. Magnetic measurements evidence the interaction among the magnetic moments located at the nanoparticle surface to be strong enough to establish a spin glass behavior. Specific heat analyses show a broad Schottky contribution, revealing the existence of a crystalline electric field. Inelastic neutron scattering analyses disclose that the splitting of the crystalline electric field levels associated with the Nd 3+ ions, as well as the spin-wave excitations that emerged below the Néel transition (T N ≈ 6 K) in polycrystalline NdCu 2 are maintained in the nanoparticle state. We have been able to isolate the scattering contribution arising from the nanoparticle surface where both crystalline electric field splitting and the collective magnetic excitations are well-defined despite the symmetry breaking. Quantitative analyses of this surface scattering reveal that finite-size effects and microstrain lead to a partial inhibition of the transitions from the ground state to the first excited level, as well as a positive shift (∼15%) of the energy associated to collective magnon excitations.
Antiferromagnetic materials are receiving renewed interest on behalf of their potential for information technologies. Recent reports have also revealed how the physics governing such magnetic arrangements and their excitations become more complex compared to traditional ferromagnetic materials, especially at the nanoscale. Here, we address two main issues that are of prime interest to their technological transfer. First, using small-angle neutron scattering, we show the existence of a magnetic helix-like super-structure in a polycrystalline TbCu2 alloy, preserved at both bulk and nanoparticle ensembles of 8 nm. Second, using inelastic neutron scattering, we elucidate the magnetic excitons and the crystalline electric field energy level schemes of TbCu2 in bulk and nanoparticle ensembles. This allows to understad the effect of the surface broken symmetry on the quantum energy levels at the nanoscale, so as the key role of interfacial effects on the propagation of magnetic excitations. Our research provides insights for the realization of magnetic moment dynamics models based on complex nanometric super-structures, and for nanoparticles to be integrated in spintronics and information technology applications.
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