Spin-glass Behavior Research Articles

Observation of Griffiths phase, spin glass behaviour and magnetocaloric effect in frustrated Ga2Mn2-xCrxO7 (x = 0, 0.1, 0.3, 0.5) pyrochlore compounds

New series of pyrochlore compounds Ga2Mn2-xCrxO7 (x = 0–0.5) has been synthesized by conventional solid-state reaction method. The X-ray diffraction analysis confirms a single-phase cubic structure of the prepared compounds. All compounds undergo a paramagnetic-antiferromagnetic transition at the Néel transition temperature, close to 42 K. Below ∼12 K temperature, magnetization measurements reveal a glassy behaviour. The value of frustration parameter indicates the presence of a spin frustration. All the compounds exhibit the Griffiths phase. The Arrott's plots confirmed a second-order magnetic phase transition. Moreover, under 5 T applied magnetic field, the maximum value of magnetic entropy change −ΔS was 1.36 J/kg.K for Ga2Mn2O7 compound, which slightly increased to 1.47 J/kg.K for the compound with x = 0.5. At 21 K, the relative cooling power value enhanced from 42.96 J/kg to 47.73 J/kg with Cr4+-ion content changing from x = 0 to x = 0.5.

Origin of spin glass magnetic behavior and phase stability of flux-grown RE(Al, Cr, Fe)B4 (RE = Ho and Er) single crystals

The YCrB4 type (α-phase, orthorhombic with space group Pbam) α-HoAlB4 and α-ErAlB4 single crystals which were self-flux grown exhibit the spin glass magnetic behavior, which is anomalous compared to the other reported rare earth system phases of α-REAlB4. Local atomic arrangements with the atomic-resolution for α-HoAlB4 and α-ErAlB4 compounds have been investigated by spherical aberration (Cs)-corrected scanning transmission electron microscopy (STEM) with high-angle annular detector dark-field (HAADF) and annular bright-field (ABF), and STEM-energy-dispersive X-ray spectroscopy (EDS) techniques to elucidate the origin of the exotic magnetic behavior. Observed HAADF- and ABF-STEM images and STEM-EDS chemical maps taken with the incident beam parallel to the [001] direction clearly indicate the existence of substitutions for Al atom sites. The phase stability of RAlB4 (R = Ho ∼ Lu) compounds was discussed from the viewpoint of crystallographic features with lattice parameters and compositions. Based on the presented results, it could be concluded that the origin of the spin glass behavior for self-flux grown α-HoAlB4 and α-ErAlB4 single crystals is the unexpected substitution of Cr/Fe atoms for Al ones. Simultaneously, the substitution by Cr/Fe atoms for Al atoms is indicated to play a significant role to stabilize the YCrB4-type α-HoAlB4 and α-ErAlB4 compounds.

The magnetic ground state of Ba(Fe1/2Sn1/2)O3-δ: A potential giant dielectric material for technological applications

Ba(Fe1/2Sn1/2)O3-δ (BFSO) is a potential environmental friendly compound for miniaturization of electronic devices as it exhibits giant dielectric constant at room temperature. However, its magnetic ground state is not settled. We present here comprehensive investigation of the as-sintered and oxygen-annealed BFSO samples using x-ray diffraction, dielectric, x-ray photoelectron spectroscopy (XPS), dc magnetization (M(T, H, t)) and specific heat measurements. Both samples crystallize in a cubic Pm-3m symmetry. At room temperature, both samples show a giant dielectric constant of the order of ε' ∼104 and two low-temperature dielectric relaxations resulting from polaron-hoping and Maxwell-Wagner effect, respectively. The temperature-dependent dc magnetization and specific heat measurements on as-sintered and oxygen-annealed BFSO samples confirm the absence of long-range ordered antiferromagnetic transition at TN ∼55 K. Further, both samples show history-dependent irreversibility of zero-field cooled warming (ZFCW) and field cooled warming (FCW) M(T) curves at the irreversibility temperature (Tirr ∼18 K) with a peak in the ZFCW M(T) curve at the spin-glass freezing temperature Tf ∼16 K. In addition, the FCW M(T) curve of both samples show plateauing over a small temperature range before it starts increasing below Tf, a characteristic typically observed in cluster/spin-glass systems. The presence of long-time magnetic relaxation and aging effect in both samples further support the spin-glass behavior. We also discussed the impact of oxygen vacancies on the physical and magnetic properties and possible origin of the glassy ground state in BFSO.

Spin Glass Behavior in Amorphous Cr2 Ge2 Te6 Phase-Change Alloy.

The layered crystal structure of Cr2 Ge2 Te6 shows ferromagnetic ordering at the two-dimensional limit, which holds promise for spintronic applications. However, external voltage pulses can trigger amorphization of the material in nanoscale electronic devices, and it is unclear whether the loss of structural ordering leads to a change in magnetic properties. Here, it is demonstrated that Cr2 Ge2 Te6 preserves the spin-polarized nature in the amorphous phase, but undergoes a magnetic transition to a spin glass state below 20K. Quantum-mechanical computations reveal the microscopic origin of this transition in spin configuration: it is due to strong distortions of the CrTeCr bonds, connecting chromium-centered octahedra, and to the overall increase in disorder upon amorphization. The tunable magnetic properties of Cr2 Ge2 Te6 can be exploited for multifunctional, magnetic phase-change devices that switch between crystalline and amorphous states.

Evidence of re-entrant spin-glass behavior in the GdAgGa compound

Evidence of re-entrant spin-glass behavior in the GdAgGa compound

Transition from AFM Spin Canting to Spin Glass-AFM Exchange as Particle Size Decreases in LaFeO3.

In this work, we have studied structural and magnetic properties of LaFeO3 as a function of the particle size d, from bulk (d >> 1 µm) to nanoscale (d ≈ 30 nm). A large number of twins were observed for large particles that disappear for small particle sizes. This could be related to the softening of the FeO6 distortion as particle size decreases. It was observed that the bulk sample showed spin canting that disappeared for d ~ 125 nm and can be associated with the smoothening of the orthorhombic distortion. On the other hand, for d < 60 nm, the surface/volume ratio became high and, despite the high crystallinity of the nanoparticle, a notable exchange effect bias appeared, originated by two magnetic interactions: spin glass and antiferromagnetism. This exchange bias interaction was originated by the formation of a "magnetic core-shell": the broken bonds at the surface atoms give place to a spin glass behavior, whereas the inner atoms maintain the antiferromagnetic G-type order. The LaFeO3 bulk material was synthesized by the ceramic method, whereas the LaFeO3 nanoparticles were synthesized by the sol-gel method; the particle size was varied by annealing the samples at different temperatures. The physical properties of the materials have been investigated by XRD, HRTEM, TGA, and AC and DC magnetometry.

Short-term memory capacity analysis of Lu3Fe4Co0.5Si0.5O12-based spin cluster glass towards reservoir computing

Reservoir computing is a brain heuristic computing paradigm that can complete training at a high speed. The learning performance of a reservoir computing system relies on its nonlinearity and short-term memory ability. As physical implementation, spintronic reservoir computing has attracted considerable attention because of its low power consumption and small size. However, few studies have focused on developing the short-term memory ability of the material itself in spintronics reservoir computing. Among various magnetic materials, spin glass is known to exhibit slow magnetic relaxation that has the potential to offer the short-term memory capability. In this research, we have quantitatively investigated the short-term memory capability of spin cluster glass based on the prevalent benchmark. The results reveal that the magnetization relaxation of Co, Si-substituted Lu3Fe5O12 with spin glass behavior can provide higher short-term memory capacity than ferrimagnetic material without substitution. Therefore, materials with spin glass behavior can be considered as potential candidates for constructing next-generation spintronic reservoir computing with better performance.

Canonical spin glass and cluster glass behavior in the polymorphs of LiFeSnO4

We report a comprehensive and comparative study of structural, static, dynamic, and nonequilibrium magnetic properties on the polymorphs of $\mathrm{LiFeSn}{\mathrm{O}}_{4}$. It exhibits two polymorphs: (i) orthorhombic phase (HT) stabilized at high temperature and (ii) hexagonal phase (LT) obtained at lower synthetic temperature. The HT phase crystallizes in the orthorhombic structure (space group: Pmcn) and exhibits a site disordered, nonfrustrated zig-zag network of ${\mathrm{Fe}}^{3+}$ and ${\mathrm{Sn}}^{4+}$ ions. On the other hand, the LT phase shows a disordered frustrated kagome network of ${\mathrm{Li}}^{1+}, {\mathrm{Fe}}^{3+}$, and ${\mathrm{Sn}}^{4+}$ ions crystallizing in the hexagonal structure (space group: $P{6}_{3}mc$). The low-temperature thermo-magnetic irreversibility and the absence of heat capacity anomaly in both polymorphs indicate the absence of long-range magnetic ordering and a possible glassy state. Zero-field-cooled and field-cooled magnetic memory effect and spin relaxation measurements stipulate the spin glass nature of the polymorphs. Further, spin glass behavior is confirmed by the AC susceptibility measurements. Interestingly, these polymorphs reveal different classes of spin glass states. The site disordered HT phase exhibits a single spin-flip time ${\ensuremath{\tau}}_{0}\ensuremath{\sim}3\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}13}$ sec, indicating a canonical spin glass state. In contrast, LT phase, which is disordered and geometrically frustrated, shows the spin-flip time of ${\ensuremath{\tau}}_{0}\ensuremath{\sim}9\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}10}$ sec, suggesting a cluster spin glass state. In addition, the exchange bias effect was observed due to magnetic inhomogeneity in both polymorphs.

Spin dynamics in ensembles of ultrafine ferrihydrite nanoparticles

Features of the spin dynamics in ensembles of interacting (FH-chem) and weakly interacting (FH-coated) magnetic ultrasmall ($\ensuremath{\langle}d\ensuremath{\rangle}\ensuremath{\sim}2$ nm) ferrihydrite nanoparticles have been explored. The dc and ac magnetic susceptibilities $[{\ensuremath{\chi}}^{\ensuremath{'}}(T)$ and ${\ensuremath{\chi}}^{\ensuremath{'}\ensuremath{'}}(T)]$ of the investigated samples have been thoroughly measured in a weak magnetic field (2 Oe) around the temperatures of superparamagnetic blocking of the nanoparticle magnetic moments (19 and 50.4 K for FH-coated and FH-chem, respectively, according to the dc magnetization data). It has been shown that the magnetic interactions between nanoparticles induce the formation of the cluster spin-glass state below the superparamagnetic blocking temperature (${T}_{g}=18$ and 49.5 K for FH-coated and FH-chem, respectively). It has been found that coating of nanoparticles increases the critical scaling index from $z\ensuremath{\nu}=5.9$ (FH-chem) to $z\ensuremath{\nu}=8.0$ (FH-coated). This indicates a general slowdown of the dynamics of correlated spins, which is also expressed as an increase in relaxation time ${\ensuremath{\tau}}_{0}$ after switching on the interparticle interactions. We attribute this phenomenon to a consequence of a change in the volume of correlated spins with the increasing size of a cluster of interacting nanoparticles. It has been demonstrated using the simulated ${\ensuremath{\chi}}^{\ensuremath{'}\ensuremath{'}}(T)$ dependence that the dissipation of the magnetic energy occurs in two independent stages. The first stage is directly related to the blocking of the nanoparticle magnetic moments, while the second stage reflects the spin-glass behavior of surface spins and depends strongly on the intensity of the interparticle interactions.

Low temperature cluster glass behavior in nanosized La0.5-xHoxCa0.5MnO3 (0 ≤ x ≤ 0.15) manganites

Dynamic magnetic properties response of La0.5-xHoxCa0.5MnO3 (0 ​= ​x ​≤ ​0.15) nanosized samples have been investigated. Temperature dependence of AC magnetic susceptibility measurements shows a broad maximum at freezing temperature Tf, suggesting the presence of spin or cluster glass behavior. For the substituted samples, a second peak can be detected below Tf and is more pronounced for x ​= ​0.15, which indicates the appearance of cluster glass behavior. The analysis of the frequency dependent peak obeys to the Vogel-Fulcher and power law, which rules out the superparamagnetic state. An unusual decrease of Tf was observed for Ho-substituted samples with increasing frequency.

Intrinsic magnetic-optical features of Dy3+ ion substituted NiCuZn nanospinel ferrites via sonochemical approach

Ni0·4Cu0·2Zn0.4DyxFe2-xO4 (x ≤ 0.10) (NCZDy) nanospinel ferrites (NSFs) were prepared by an ultrasonication approach assisted sol-gel synthesis methodology. The cubic spinel structures of products were verified by XRD (X-ray powder diffraction) study. Intrinsic vibrational absorption bands of nanoparticles for their octahedral band (υ2) at 417 cm−1 and tetrahedral (υ1) band at 563-580 cm−1 were detected by FT-IR (Fourier-transform infrared) analysis. Magnetic studies by VSM (Vibrating sample magnetometry) confirmed the soft ferromagnetic nature of all products at 15 K and 300 K temperatures. As the amount of Dy3+ rises, saturation and remanent magnetization (Ms and Mr) values first increase for x = 0.02 composition; then they start to decrease with further rising the Dy3+ content. FC (Field-cooled) and ZFC (zero field-cooled) magnetization studies reveal that the irreversible temperature is above 300 K and the samples display spin glass behavior. Mössbauer spectra (MOS) were acquired to calculate hyperfine parameters by room-temperature (RT) spectra fitting and results indicated Dy3+ ions occupy octahedral sites. The optical investigation showed NCZDy (x ≤ 0.10) NSFs carry out a direct band character, and band gap values lay between 1.69 and 2.33 eV. All samples absorb the light within the visible region which is evident from the % Diffuse Reflectance Spectroscopy (DRS) results.

Effects of Cr doping on the magnetic properties of one-dimensional spin chain system α–CoV2O6

This study investigates the structural and magnetic properties of α–CoV2O6 and Cr doped α–CoV2O6 samples synthesized using a wet chemical method. X-ray diffraction (XRD) measurements and analysis indicate that α–CoV2O6 forms in a monoclinic crystal structure, with lattice parameters a = 9.26 Å, b = 3.50 Å, c = 6.62 Å, β = 111.42°, and α = γ = 90°. The magnetic properties of the compounds were probed using a vibrating sample magnetometer (VSM), by measuring the temperature, T, field, μ0H, and time, t, dependence of magnetization, M. The compounds take on an antiferromagnetic (AFM) order at 0.1 T, with an enhancement of the magnetization below 6.5 K. Cr doping resulted in an enhancement of magnetization below TN. M(μ0H) isotherms show metamagnetic transitions with a 1/3 magnetization plateau for both samples. A large hysteresis is observed for fields less than 5 T and is attributed to frozen metastable, irreversible states. M(T) data at 2.5 T and 5 T shows that the metamagnetic transitions take both compounds from an AFM to an intermediate ferrimagnetic (FI) state and ferromagnetic (FM) state at high fields. No significant changes in TN were observed with Cr doping. Zero-field-cooled (ZFC) and field-cooled (FC) bifurcation was observed for fields between 1 T and 3 T, attributed to spin-glass-like freezing of the samples at TSG. The spin-glass behaviour of the samples was confirmed using the Gabay-Toulouse (G-T) line and M(t) curves.

Exchange bias effect and inhomogeneous magnetism in 6H Ba3CoFeRuO9: Role of structural site disorder

Structural, magnetic, electrical and thermal investigations on ternary barium ruthenate Ba3CoFeRuO9 (BCFRO) reveal the role of the two different octahedral B-site in creating locally varying competing antiferromagnetic and ferromagnetic interactions. BCFRO forms in 6H hexagonal structure in the P63/mmc space group. Neutron diffraction and specific heat capacity measurements affirmed the absence of any long-range ordering and structural transition in the compound. DC thermomagnetic studies evidences spin glass magnetism with Tg ∼ 50 K. A large exchange bias (EB) field of 3.48 kOe is obtained at 3 K under a cooling field of 50 kOe. Careful analysis indicates, EB in our system stems from inhomogeneous magnetism owing to spatially varying chemical composition. Competing ferromagnetic and antiferromagnetic phases giving rise to spin glass behaviour is the manifestation of site disorder induced by mixed valences of magnetic ions. The exchange bias training effect in our system follows spin relaxation model of rotatable and frozen spins which are exchange coupled at the interface. Strong electron localisation occurs by virtue of the specific 6H structure with corner shared octahedral 2a site and face shared octahedral 4f site. The electrical and thermal transport in BCFRO follows Efros-Shklovskii variable range hopping (ES VRH) model below 150 K. The high resistivity of BCFRO at low temperatures is also reflected in the low thermal conductivity and huge Seebeck coefficient.

Ferrimagnetic and spin glass behaviour in SrMn2+3Ti4+14M3+4O38 (M = Ti and Fe) synthetic crichtonites.

Novel SrMn3Ti14M4O38 (M = Ti and Fe) compounds with a crichtonite-type structure are reported herein. M = Ti shows a ferrimagnetic behavior at TN = 15 K, while M = Fe creates a ferromagnetic cluster-glass at Tf = 8 K via positional disorder. This family offers a promising magnetic playground.

Spin-glass behavior and redox catalytic properties of room temperature produced ZnCrMnO4

Recognizing the multifunctional capability of spinels, synthesis, and properties of oxide spinel with an equal concentration of Jahn Teller active Mn 3+ and geometrically frustrated Cr 3+ with non-magnetic Zn 2+ have been explored. ZnCrMnO 4 , resulting from the room temperature oxidation reaction, has an average crystallite size of 16 nm. Nearly 25% of Zn occupies the octahedral sites along with Cr and Mn, as revealed by the successful structural refinement in the Fd-3m space group. Electron microscopic results confirm cubic spinel formation. Raman spectrum shows the disordered nature of the spinel. X-ray photoelectron spectral (XPS) analysis establishes mixed valences of manganese ((III), (IV)) and chromium ((III) and (VI)). ZnCrMnO 4 displays electronic transitions typical of Mn 3+ and Cr 3+ in its UV–Visible diffuse reflectance spectrum. Spin-glass frustration at 26 K, followed by an antiferromagnetic ordering at 10 K, is noticed for the sample from the magnetic measurements. The sample exhibits a surface area of 138 m 2 /g (BET measurements) and catalyzes the oxidation of aromatic alcohols (phenol, benzyl alcohol) and reduction of nitroaromatics efficiently.

Magnetic properties of double perovskite oxide Gd1.8Ce0.2NiMnO6

In this paper, a double perovskite oxide Gd1.8Ce0.2NiMnO6 polycrystalline sample was prepared using a conventional high temperature and solid-state reaction method. The phase formation of sample was examined using X-ray diffractometry, and the magnetic properties were measured using a PPMS. The results showed that the sample was monophase and had a space group of monoclinic P21/n. At T &gt; TG the sample was purely paramagnetic. At TC &lt; T &lt; TG paramagnetic and ferromagnetic states coexisted, and Griffiths-like phase appeared in the sample. In the lower temperature region (T &lt; TN) there was competition between ferromagnetic and antiferromagnetic states, and cluster spin-glass behavior appeared. When a magnetic field of 7 T was applied, the double perovskite oxide Gd1.8Ce0.2NiMnO6 showed a maximum −ΔSM value of 3.12296 J · kg−1 · K−1 near Curie temperature with an RCP (Refrigeration Cooling Performance) of 231.09904 J/kg. Analysis of the Arrott, recalibration and Loop curves all proved that the sample underwent a second-order phase transition.

2D spin glass MnIn2Se4: application of liquid-phase exfoliation to a layered structure with seven-atom-thick layers

Liquid-phase exfoliation of a layered-structure semiconductor, MnIn2Se4, followed by sequential centrifugation, affords nanosheets of variable thicknesses. Both the bulk material and nanosheets exhibit spin-glass behavior with spin freezing at ∼3 K.

Nickel substitution induced reentrant spin glass behavior in EuGa4

Typically, atomic scale disorder is essential to show glassy behavior and amorphous materials can be the optimum candidates in this regard. Generating local disorder in an ordered material by substitution of another metal is a challenging task. In this paper, we successfully substituted Ni in ${\mathrm{EuGa}}_{4}$ (${\mathrm{EuNi}}_{0.37}{\mathrm{Ga}}_{3.63}$) to induce spin glass (SG) behavior. The compound was characterized by single-crystal x-ray diffraction, dc magnetization, frequency-dependent ac susceptibility, isothermal magnetization at various temperatures, spin relaxation, specific heat, and electric resistivity. Two distinct anomalies were observed in dc susceptibility $\ensuremath{\sim}16.5$ and 5.2 K corresponding to long-range antiferromagnetic (AFM) ordering and SG transition, respectively. Their characteristic peaks in specific heat capacity further support the AFM and SG behavior. The irreversibility temperature is fitted with the Almeida-Thouless equation, confirming the Ising SG. The SG behavior is further confirmed by shift of maxima to a high temperature in ac susceptibility with increasing frequency. Nonzero spin relaxation after 7200 s, fitted with stretched exponential model, provides the value of $\ensuremath{\beta}=0.41$. This material can be identified as a possible reentrant SG as AFM and SG behavior coexist in the low-temperature range. Additionally, a spin-flip transition is observed in the AFM region ($5.2\phantom{\rule{0.28em}{0ex}}\mathrm{K}&lt;T&lt;16.5\phantom{\rule{0.28em}{0ex}}\mathrm{K}$). Our first-principles calculations show Ni substitution induces the distortion in electronic band structure as compared with parent ${\mathrm{EuGa}}_{4}$. A minimal difference between the different magnetic configurations for Ni-substituted ${\mathrm{EuGa}}_{4}$ suggests the frustration in the lattice, pointing toward SG behavior.

The Effect of Co-Doping on the Structural and Magnetic Properties of Single-Domain Crystalline Copper Ferrite Nanoparticles

Nanoparticles of Co-doped copper ferrite, Cu0.75Co0.25Fe2O4, were successfully synthesized by hydrothermal method. The preparation conditions were optimized to produce small nanoparticles with crystallite size of 20 nm that fall into the single-domain regime. The influence of Co-doping on the structure and magnetic properties of pure copper ferrite, CuFe2O4, was investigated. The prepared ferrite nanoparticles were found to be in a single structural phase with a spinel-type structure, according to the XRD and FT-IR measurements. When compared to pure Cu ferrite, the addition of Co increased the lattice constant and decreased the density. The TEM results confirmed the spherical morphology of the prepared ferrite nanoparticles. For the entire temperature range of the ferrite nanoparticles, the magnetization measurements showed a single ferrimagnetic phase. It was observed that the coercivity and remanent magnetization increased with decreasing temperature. Magnetic anisotropy was found to increase with Co-doping in comparison to pure Cu ferrite. The ZFC–FC magnetization curves showed that the blocking temperature (TB) of the prepared nanoparticles is above room temperature, demonstrating that they are ferrimagnetic at room temperature and below. Additionally, it was found that decreasing the magnetic field lowers TB. The FC curves below TB were observed to be nearly flat, indicating spin-glass behavior that might be attributed to nanoparticle interactions and/or surface effects such as spin canting and spin disorder.

The missing link between zeolites and polyoxometalates.

Open framework materials such as zeolites and metalorganic frameworks are garnering tremendous interest because of their intriguing architecture and attractive functionalities. Thus, new types of open framework materials are highly sought after. Here, we present the discovery of completely new inorganic framework materials, where, in contrast to conventional inorganic open frameworks, the scaffold is not based on tetrahedral EO4 (E = main group element) but octahedral MO6 (M = transition metal) building blocks. These structural features place them closer to polyoxometalates than zeolites. The first representatives of this class of materials are [(R)24(NH4)14(PO(OH)2)6]·[M134(PO3(OH,F))96F120] (M = Co, R = C2Py = 1-ethylpyridinium and M = Ni, R = C4C1Py = 1-butyl-3-methylpyridinium) featuring interlinked fullerene-like nanosphere cavities. Having a transition metal building up the framework brings about interesting properties, for example, spin-glass behavior, and, with this particular topology, a hedgehog-like spin orientation.