Bulk Magnetometry Research Articles

Tailoring magnetism in chromium-doped zinc cobalt ferrite nanostructure for advanced spintronic memory devices

Soft magnetic ferrites serve as a crucial component in a wide array of sensing and actuating applications across various industries, including consumer electronics, automotive systems, spintronics, and more. These materials also find utility in spintronics, particularly for next-generation magnetic random-access memory (MRAM) due to their excellent inductive properties, which enhance the performance and scalability of spintronic memory devices. This study focuses on fine-tuning soft magnetic ferrites for inductive applications by doping them with Cr ions. By utilizing advanced experimental techniques such as the vibrating sample magnetometer (VSM) for bulk magnetometry and X-ray magnetic circular dichroism (XMCD) alongside X-ray absorption spectroscopy for atomic studies, the research aims to investigate the structural, electronic, and magnetic properties of the nanoferrites. Addition of doping in the soft ferrites observes reduction in the general magnetic parameters, with the only exception being coercivity, which decreases from 381 Oe to 275 Oe as the doping concentration increases from x = 0 to x = 0.02, and then increases to 350 Oe at x = 0.03. Through such precise tuning of the nanoparticles, this study aims to investigate the controllable soft magnetic properties of the nanoferrites, thereby paving the way for fast access times, non-volatility, and low energy consumption, presenting a compelling alternative to conventional memory technologies.

The Role of Interfacial Interactions and Oxygen Vacancies in Tuning Magnetic Anisotropy in LaCrO3/LaMnO3 Heterostructures

AbstractThe interplay of lattice, electronic, and spin degrees of freedom at epitaxial complex oxide interfaces provides a route to tune their magnetic ground states. Unraveling the competing contributions is critical for tuning their functional properties. The relationship between magnetic ordering and magnetic anisotropy and the lattice symmetry, oxygen content, and film thickness in compressively strained LaMnO3 (LMO)/LaCrO3 (LCO) superlattices is investigated. Mn–O–Cr antiferromagnetic superexchange interactions across the heterointerface result in a net ferrimagnetic magnetic structure. Bulk magnetometry measurements reveal isotropic in‐plane magnetism for as‐grown oxygen‐deficient thin samples due to equal fractions of orthorhombic a+a‐c‐, and a‐a+c‐ twin domains. As the superlattice thickness is increased, in‐plane magnetic anisotropy emerges as the fraction of the a+a‐c‐ domain increases. On annealing in oxygen, the suppression of oxygen vacancies results in a contraction of the lattice volume, and an orthorhombic to rhombohedral transition leads to isotropic magnetism independent of the film thickness. The complex interactions are investigated using high‐resolution synchrotron diffraction and X‐ray absorption spectroscopy. These results highlight the role of the evolution of structural domains with film thickness, interfacial spin interactions, and oxygen‐vacancy‐induced structural phase transitions in tuning the magnetic properties of complex oxide heterostructures.

Controlling Noncollinear Ferromagnetism in van der Waals Metal-Organic Magnets.

Van der Waals (vdW) magnets both allow exploration of fundamental 2D physics and offer a route toward exploiting magnetism in next generation information technology, but vdW magnets with complex, noncollinear spin textures are currently rare. We report here the syntheses, crystal structures, magnetic properties and magnetic ground states of four bulk vdW metal-organic magnets (MOMs): FeCl2(pym), FeCl2(btd), NiCl2(pym), and NiCl2(btd), pym = pyrimidine and btd = 2,1,3-benzothiadiazole. Using a combination of neutron diffraction and bulk magnetometry we show that these materials are noncollinear magnets. Although only NiCl2(btd) has a ferromagnetic ground state, we demonstrate that low-field hysteretic metamagnetic transitions produce states with net magnetization in zero-field and high coercivities for FeCl2(pym) and NiCl2(pym). By combining our bulk magnetic data with diffuse scattering analysis and broken-symmetry density-functional calculations, we probe the magnetic superexchange interactions, which when combined with symmetry analysis allow us to suggest design principles for future noncollinear vdW MOMs. These materials, if delaminated, would prove an interesting new family of 2D magnets.

Slow magnetic relaxation in a europium(II) complex.

Single-ion anisotropy is vital for the observation of Single-Molecule Magnet (SMM) properties (i.e., a slow dynamics of the magnetization) in lanthanide-based systems. In the case of europium, the occurrence of this phenomenon has been inhibited by the spin and orbital quantum numbers that give way to J = 0 in the trivalent state and the half-filled population of the 4f orbitals in the divalent state. Herein, by optimizing the local crystal field of a quasi-linear bis(silylamido) EuII complex, the [EuII(N{SiMePh2}2)2] SMM is described, providing an example of a europium complex exhibiting slow relaxation of its magnetization. This behavior is dominated by a thermally activated (Orbach-like) mechanism, with an effective energy barrier of approximately 8 K, determined by bulk magnetometry and electron paramagnetic resonance. Ab initio calculations confirm second-order spin-orbit coupling effects lead to non-negligible axial magnetic anisotropy, splitting the ground state multiplet into four Kramers doublets, thereby allowing for the observation of an Orbach-like relaxation at low temperatures.

Probing temperature-dependent magnetism in cobalt and zinc ferrites: A study through bulk and atomic-level magnetic measurements for spintronics

Spinel ferrites (MFe2O4) are integral to various industries, particularly spintronics, which utilizes the intrinsic spin of electrons as well as the electronic charge to develop devices that dictate spin-based transport, advancing new memory, logic applications, and improving magnetic storage technologies. These materials are valued for their exceptional optical, magnetic and electrical properties, and their easily tunable shape and size. This flexibility of spinel ferrites and their connection to the material’s magnetic behavior can be investigated by studying a range of spinel ferrite structures. In this study, the magnetic behaviors of cobalt ferrite (CFO) and zinc ferrite (ZFO) nanoparticles were examined using a vibrating sample magnetometer (VSM, bulk magnetometry) and X-ray Magnetic Circular Dichroism (XMCD, atomic magnetometry). The Rietveld refinement of XRD data supported single phase spinel structure, while X-ray Absorption Spectroscopy (XAS), particularly through the Co L-edge XANES analysis, detected both Co2+ and Co3+ ions in CFO, suggesting significant ferromagnetic behavior due to octahedral site occupation. In contrast, ZFO exhibited antiferromagnetic character, with Zn2+ ions in tetrahedral sites, and canted antiferromagnetism manifesting as a hysteresis loop below 300 K, potentially related to lattice distortions or strain. At the atomic scale, XMCD analysis, along with sum rules, estimated the average magnetic moments for cobalt and zinc ferrites to be 3.045 ± 0.1 (1.448 ± 0.1) and 0.657 ± 0.1 (2.12 ± 0.1) μB at temperatures of 300 K (90 K), respectively. However, VSM-based bulk measurements indicated magnetic moments of 2.566 (2.288) and 0.281 × 10−3 (0.6503 × 10−3) μB for CFO and ZFO, respectively, at the same temperatures. The observed variation between bulk and atomic-scale magnetic moments points to complex interstitial interactions within the spinel ferrite’s sublattices. This discrepancy between the atomic-scale and bulk magnetic moments suggests intricate interstitial interactions within the spinel ferrite’s sublattices. These insights into the structural and magnetic intricacies of spinel ferrite nanoparticles enhance our understanding, facilitating the design of cutting-edge spintronic devices.

Tuning strategy for Curie-temperature enhancement in the van der Waals magnet Mn1+xSb2−xTe4

The van-der-Waals antiferromagnetic topological insulator MnBi2Te4 is one of the few materials that realize the sought-after quantum anomalous Hall (QAH) state and quantized surface charge transport. To assess the relevance of its isostructural analog MnSb2Te4 as a potential QAH candidate, the roles of Mn/Sb site mixing and cationic vacancies need to be clarified. Recent findings have shown that non-stoichiometry in Mn1±xSb2∓xTe4 is an efficient tuning knob to achieve a net spin-polarized state and to raise the magnetic ordering temperature well above that of MnBi2Te4. Here, we report the crystal structure, the bulk and the surface magnetism of two new Mn1+xSb2−xTe4 samples: Mn1.08Sb1.92Te4(x ≈ 0.1) with TC = 44 K, and Mn2.01Sb1.19Te4(x ≈ 1.0) with the record TC = 58 K. We quantify the site mixing comprehensively by combining various structural probes on powders and single crystals, and then employ bulk, local (electron spin resonance), and spectroscopic (x-ray magnetic circular dichroism) probes to connect these insights to the magnetism of these materials. We demonstrate that Mn over-stoichiometry up to x = 1.0, in combination with a particular Mn/Sb intermixing pattern and the increasingly three-dimensional character of the magnetic order, push the TC upwards. The tendency towards more robust ferromagnetism mediated by stronger interlayer exchange in Mn1+xSb2−xTe4 upon increasing x is confirmed by bulk magnetometry and by a series of density-functional-theory calculations of model structures with varying intermixing.

Large ordered moment with strong easy-plane anisotropy and vortex-domain pattern in the kagome ferromagnet Fe3Sn

We report the magnetic anisotropy of kagome bilayer ferromagnet Fe3Sn probed by the bulk magnetometry and magnetic force microscopy (MFM) on high-quality single crystals. The dependence of magnetization on the orientation of the external magnetic field reveals strong easy-plane magnetocrystalline anisotropy and anisotropy of the saturation magnetization. The leading magnetocrystalline anisotropy constant shows a monotonous increase from K1≈−1.0×106 J/m3 at 300 K to −1.3×106 J/m3 at 2 K. Our ab initio electronic structure calculations yield the value of total magnetic moment of 7.1 μB/f.u. and a magnetocrystalline anisotropy energy density of −0.57 meV/f.u. (−1.62×106J/m3) both being in reasonable agreement with the experimental values. The MFM imaging reveals micrometer-scale magnetic vortices with weakly pinned cores that vanish at the saturation field of ∼3 T applied perpendicular to the kagome plane. The observed vortex-domain structure is well reproduced by the micromagnetic simulations, using the experimentally determined value of the anisotropy and exchange stiffness.

Non-collinear magnetism in the post-perovskite thiocyanate frameworks CsM(NCS)3.

AMX3 compounds are structurally diverse, a notable example being the post-perovskite structure which adopts a two-dimensional framework with corner- and edge-sharing octahedra. Few molecular post-perovskites are known and of these, none have reported magnetic structures. Here we report the synthesis, structure and magnetic properties of molecular post-perovskites: CsNi(NCS)3, a thiocyanate framework, and two new isostructural analogues CsCo(NCS)3 and CsMn(NCS)3. Magnetisation measurements show that all three compounds undergo magnetic order. CsNi(NCS)3 (Curie temperature, T C = 8.5(1) K) and CsCo(NCS)3 (T C = 6.7(1) K) order as weak ferromagnets. On the other hand, CsMn(NCS)3 orders as an antiferromagnet (Néel temperature, T N = 16.8(8) K). Neutron diffraction data of CsNi(NCS)3 and CsMn(NCS)3, show that both are non-collinear magnets. These results suggest molecular frameworks are fruitful ground for realising the spin textures required for the next generation of information technology.

γ-BaFe2O4: a fresh playground for room temperature multiferroicity

Multiferroics, showing the coexistence of two or more ferroic orderings at room temperature, could harness a revolution in multifunctional devices. However, most of the multiferroic compounds known to date are not magnetically and electrically ordered at ambient conditions, so the discovery of new materials is pivotal to allow the development of the field. In this work, we show that BaFe2O4 is a previously unrecognized room temperature multiferroic. X-ray and neutron diffraction allowed to reveal the polar crystal structure of the compound as well as its antiferromagnetic behavior, confirmed by bulk magnetometry characterizations. Piezo force microscopy and electrical measurements show the polarization to be switchable by the application of an external field, while symmetry analysis and calculations based on density functional theory reveal the improper nature of the ferroelectric component. Considering the present findings, we propose BaFe2O4 as a Bi- and Pb-free model for the search of new advanced multiferroic materials.

Transformation of BiFeO3 magnetic properties by Eu doping: magnetometry and Mössbauer studies

This paper reports the results of investigations the effect of doping of bismuth ferrite with europium ions on its magnetic properties. Combined studies by structural (X-ray diffraction), local probe (151Eu, 57Fe Mössbauer spectroscopy), and bulk magnetometry (vibration sample magnetometry) methods allow a deeper understanding of the magnetic response modification mechanisms in the Bi1-xEuxFeO3 system. It was found that Eu doping in the range of x ​< ​0.15 leads to smooth variation of R3c crystal structure parameters, but for x ​> ​0.15 crystal structure changes to Pn21a. Bulk and local magnetic properties are also sensitive to these modifications in the crystal structure. For instance, BiFeO3 shows antiferromagnetic response, whereas bulk ferromagnetic response appears in Bi0.8Eu0.2FeO3.

Magnetism on the stretched diamond lattice in lanthanide orthotantalates

The magnetic Ln$^{3+}$ ions in the fergusonite and scheelite crystal structures form a distorted or stretched diamond lattice which is predicted to host exotic magnetic ground states. In this study, polycrystalline samples of the fergusonite orthotantalates $M$-LnTaO$_4$ (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er) are synthesized and then characterized using powder diffraction and bulk magnetometry and heat capacity. TbTaO$_4$ orders antiferromagnetically at 2.25 K into a commensurate magnetic cell with $\vec{k}=0$, magnetic space group 14.77 ($P2_1$$'/c$) and Tb moments parallel to the $a$-axis. No magnetic order was observed in the other materials studied, leaving open the possibility of exotic magnetic states at $T<2$ K.

Polarized neutron reflectometry characterization of interfacial magnetism in an FePt/FeRh exchange spring

We report on the depth-sensitive, temperature-dependent exchange coupling in an FePt/FeRh thin-film exchange-spring structure. The depth-dependent in-plane magnetization is measured as a function of applied magnetic field and sample temperature using polarized neutron reflectometry (PNR). The magnetization profiles are interpreted in terms of the competition between anisotropy, exchange coupling, and dipolar coupling as the FeRh undergoes the magnetic phase transition from antiferromagnetic to ferromagnetic ordering. The PNR data are combined with bulk magnetometry and x-ray characterization, allowing us to determine characteristic length scales over which the exchange-spring mechanism is effective at ambient and elevated temperatures.

Mapping the magnetic state as a function of antisite disorder in Sm2NiMnO6 double perovskite thin films

The predictability of any characteristic functional aspect in a double perovskite system has always been compromised by its strong dependence over the inevitably present anti-site disorders (ASD). Here, we aim to precisely map the quantitative and qualitative nature of ASD with the corresponding modifications in observables describing the magnetic and electronic state in epitaxial Sm$ _{2} $NiMnO$ _{6} $ (SNMO) double perovskite thin films. The concentration and distribution patterns of ASD are effectively controlled by optimizing growth conditions and estimated on both local and global scales utilizing extended X-ray absorption fine structure and bulk magnetometry. Depending upon the defect densities, the nature of disorder distribution can vary from homogeneous to partially segregated patches. Primarily, the effect of varying B-site cationic arrangement in SNMO is reflected as the competition of long range ferromagnetic (FM) and short scale antiferromagnetic (AFM) interactions originated from ordered Ni-O-Mn and disordered Ni-O-Ni or Mn-O-Mn bonds, respectively, which leads to systematic shift in magnetic transition temperature and drastic drop in saturation magnetization. In addition, we have observed that the gradual increment in density of ASD leads to significant deviation from uniaxial anisotropy character, reduction in anisotropy energy and enhancement of moment pinning efficiency. However, the observed signatures of $ Ni^{2+}+Mn^{4+} \longrightarrow Ni^{3+}+Mn^{3+} $ charge disproportionation is found to be independent of cation disorder densities. This work serves as a basic route-map to tune the characteristic magnetic anisotropy, magnetic phase transitions, and magnetization reversal mechanism by controlling ASD in a general double perovskite system.

Occupancy disorder in the magnetic topological insulator candidate Mn1−x Sb2+x Te4

Abstract MnSb2Te4 is a candidate magnetic topological insulator exhibiting more pronounced cation intermixing than its predecessor MnBi2Te4. Investigating the cation intermixing and its possible implications on the magnetic order in MnSb2Te4 are currently hot topics in research on quantum materials for spintronics and energy-saving applications. Two single-crystal X-ray diffraction measurements of Mn1−x Sb2+x Te4 (x = 0.06 and x = −0.1) are presented alongside a detailed discussion of its crystal structure with a spotlight on the apparent occupancy disorder between the two cations. This disorder has been noted by other groups as well, yet never been analyzed in-depth with single-crystal X-ray diffraction. The latter is the tool of choice to receive a meaningful quantification of antisite disorder. Between the two synthesis procedures we find subtle differences in phases and/or alternation of the cation content which has implications on the magnetic order, as illustrated by bulk magnetometry. Understanding and assessing this disorder in magnetic topological insulators of the MnX2Te4 (X = Bi, Sb) type is crucial to gauge their applicability for modern spintronics. Furthermore, it opens new ways to tune the “chemical composition – physical property” relationship in these compounds, creating an alluring aspect also for fundamental science.

Asymmetric Interfacial Intermixing Associated Magnetic Coupling in LaMnO3/LaFeO3 Heterostructures

The structural and magnetic properties of LaMnO3/LaFeO3 (LMO/LFO) heterostructures are characterized using a combination of scanning transmission electron microscopy, electron energy-loss spectroscopy, bulk magnetometry, and resonant x-ray reflectivity. Unlike the relatively abrupt interface when LMO is deposited on top of LFO, the interface with reversed growth order shows significant cation intermixing of Mn3+ and Fe3+, spreading ∼8 unit cells across the interface. The asymmetric interfacial chemical profiles result in distinct magnetic properties. The bilayer with abrupt interface shows a single magnetic hysteresis loop with strongly enhanced coercivity, as compared to the LMO plain film. However, the bilayer with intermixed interface shows a step-like hysteresis loop, associated with the separate switching of the “clean” and intermixed LMO sublayers. Our study illustrates the key role of interfacial chemical profile in determining the functional properties of oxide heterostructures.

Homogeneity of the negatively charged assembly of nitrogen vacancy centres in diamonds using the Quasi-finite-element optical scanning position method

We developed a versatile Quasi-finite-element scanning method to analyse the concentration and homogeneity of the ensembles of nitrogen-vacancy (NV−) centres in block diamonds. In this method, area of the bulk diamond with high-density NV− centres was divided into small pieces at the nanoscale by using a focused light beam. The concentration of NV− centres was obtained and imaged through the fluorescence intensity of each pixel by employing a home-built spectrometer. In addition, global and local homogeneities were introduced to evaluate the NV− centre distribution. NV− centres in a specific pixel exhibited preferred direction growth peaks attributed to the diamond crystal orientation. Moreover, the uniformity of NV− centres was not proportional to the electron irradiation duration, but an optimal time was observed. This study can be beneficial for enhancing the sensitivities of bulk magnetometry based on confocal systems.

Bulk and element-specific magnetism of medium-entropy and high-entropy Cantor-Wu alloys

Magnetic Compton scattering, x-ray magnetic circular dichroism spectroscopy and bulk magnetometry measurements are performed on a set of medium (NiFeCo and NiFeCoCr) and high (NiFeCoCrPd and NiFeCoCrMn) entropy Cantor-Wu alloys. The bulk spin momentum densities determined by magnetic Compton scattering are remarkably isotropic, and this is a consequence of the smearing of the electronic structure by disorder scattering of the electron quasiparticles. Non-zero x-ray magnetic circular dichroism signals are observed for every element in every alloy indicating differences in the populations of the majority and minority spin states implying finite magnetic moments. When Cr is included in the solid solution, the Cr spin moment is unambiguously antiparallel to the total magnetic moment, while a vanishingly small magnetic moment is observed for Mn, despite calculations indicating a large moment. Some significant discrepancies are observed between the experimental bulk and surface magnetic moments. Despite the lack of quantitative agreement, the element specific surface magnetic moments seem to be qualitatively reasonable.

Incipient antiferromagnetism in the Eu-doped topological insulatorBi2Te3

Rare earth ions typically exhibit larger magnetic moments than transition metal ions and thus promise the opening of a wider exchange gap in the Dirac surface states of topological insulators. Yet, in a recent photoemission study of Eu-doped Bi$_2$Te$_3$ films, the spectra remained gapless down to $T = 20\;\text{K}$. Here, we scrutinize whether the conditions for a substantial gap formation in this system are present by combining spectroscopic and bulk characterization methods with theoretical calculations. For all studied Eu doping concentrations, our atomic multiplet analysis of the $M_{4,5}$ x-ray absorption and magnetic circular dichroism spectra reveals a Eu$^{2+}$ valence and confirms a large magnetic moment, consistent with a $4f^7 \; {^8}S_{7/2}$ ground state. At temperatures below $10\;\text{K}$, bulk magnetometry indicates the onset of antiferromagnetic (AFM) ordering. This is in good agreement with density functional theory, which predicts AFM interactions between the Eu impurities. Our results support the notion that antiferromagnetism can coexist with topological surface states in rare-earth doped Bi$_2$Te$_3$ and call for spectroscopic studies in the kelvin range to look for novel quantum phenomena such as the quantum anomalous Hall effect.

Optimization of a Diamond Nitrogen Vacancy Centre Magnetometer for Sensing of Biological Signals

Sensing of signals from biological processes, such as action potential propagation in nerves, are essential for clinical diagnosis and basic understanding of physiology. Sensing can be performed electrically by placing sensor probes near or inside a living specimen or dissected tissue using well established electrophysiology techniques. However, these electrical probe techniques have poor spatial resolution and cannot easily access tissue deep within a living subject, in particular within the brain. An alternative approach is to detect the magnetic field induced by the passage of the electrical signal, giving the equivalent readout without direct electrical contact. Such measurements are performed today using bulky and expensive superconducting sensors with poor spatial resolution. An alternative is to use nitrogen vacancy (NV) centres in diamond that promise biocompatibilty and high sensitivity without cryogenic cooling. In this work we present advances in biomagnetometry using NV centres, demonstrating magnetic field sensitivity of approximately 100 pT/$\sqrt{Hz}$ in the DC/low frequency range using a setup designed for biological measurements. Biocompatibility of the setup with a living sample (mouse brain slice) is studied and optimized, and we show work toward sensitivity improvements using a pulsed magnetometry scheme. In addition to the bulk magnetometry study, systematic artifacts in NV-ensemble widefield fluorescence imaging are investigated.

Extremely well isolated two-dimensional spin- 12 antiferromagnetic Heisenberg layers with a small exchange coupling in the molecular-based magnet CuPOF

We report on a comprehensive characterization of the newly synthesized Cu$^{2+}$-based molecular magnet [Cu(pz)$_2$(2-HOpy)$_2$](PF$_6$)$_2$ (CuPOF), where pz = C$_4$H$_4$N$_2$ and 2-HOpy = C$_5$H$_4$NHO. From a comparison of theoretical modeling to results of bulk magnetometry, specific heat, $\mu^+$SR, ESR, and NMR spectroscopy, this material is determined as an excellent realization of the 2D square-lattice $S=1/2$ antiferromagnetic Heisenberg model with a moderate intraplane nearest-neighbor exchange coupling of $J/k_\mathrm{B} = 6.80(5)$ K, and an extremely small interlayer interaction of about 1 mK. At zero field, the bulk magnetometry reveals a temperature-driven crossover of spin correlations from isotropic to $XY$ type, caused by the presence of a weak intrinsic easy-plane anisotropy. A transition to long-range order, driven by the low-temperature $XY$ anisotropy under the influence of the interlayer coupling, occurs at $T_\mathrm{N} = 1.38(2)$ K, as revealed by $\mu^+$SR. In applied magnetic fields, our $^1$H-NMR data reveal a strong increase of the magnetic anisotropy, manifested by a pronounced enhancement of the transition temperature to commensurate long-range order at $T_\mathrm{N} =2.8$ K and 7 T.