Spin-liquid state with precursor ferromagnetic clusters interacting antiferromagnetically in frustrated glassy tetragonal spinel Zn0.8Cu0.2FeMnO4

Abstract

Spinels (AB 2O4) with magnetic ions occupying only the octahedral B sites have inherent magnetic frustration which inhibits magnetic long-range order (LRO) but may lead to exotic states. Here we report on the magnetic properties of the tetragonal spinel Zn0.8Cu0.2FeMnO4, the tetragonality resulting from the Jahn–Teller active Mn3+ ions. X-ray diffraction and x-ray photoelectron spectroscopy of the sample yielded the composition () A [] B O4‒δ . Analysis of the temperature dependence of magnetization (M), ac magnetic susceptibilities (χ′ and χ′′), dc susceptibility (χ), heat capacity Cp , and neutron diffraction (ND) measurements show complex temperature-dependent short-range order (SRO) but without LRO. The data of χ vs. T fits the Curie–Weiss law: χ = C/(T ‒ θ) from T = 250 K to 400 K with θ ≃ 185 K signifying dominant ferromagnetic (FM) coupling with the FM exchange constant J/k B = 17 K, and C = 3.29 emu K mol‒1 Oe‒1 yielding an effective magnetic moment µ eff = 5.13 µ B resulting from the high-spin states of Cu2+ (A site) and Fe2+ (B site), while the B site trivalent ions Mn3+ and Fe3+ are in their low-spin states. The extrapolated saturation magnetization obtained from the M vs. H data at T = 2 K is explained using the spin arrangement (Cu2+↓) A [Fe2+↑, Fe3+↓, Mn3+↑] B leading to FM clusters interact antiferromagnetically at low temperatures. Temperature dependence of d(χT)/dT shows the onset of ferrimagnetism below ∼100 K and peaks near 47 K and 24 K. The relaxation time τ obtained from temperature and frequency dependence of χ″ when fit to the power law and Vogel–Fulcher laws confirm the cluster spin-glass (SG) state. The magnetic field dependence of the SG temperature follows the equation: with T SG (0) = 46.6 K, A = 8.6 × 10‒3 Oe‒0.593 and = 3.37. The temperature dependence of hysteresis loops yields coercivity HC ∼ 3.8 kOe at 2 K without exchange-bias, but HC decreases with increase in T becoming zero above 24 K, the T SG(H) for H = 800 Oe. Variations of Cp vs. T from 2 K to 200 K in H = 0 and H = 90 kOe do not show any peak characteristic of LRO. However, after correcting for the lattice contribution, a broad weak peak typically of SRO becomes evident centered around 40 K. For T < 9 K, Cp varies as T2 ; a typical signature of spin-liquids (SLs). Comparison of the ND measurements at 1.7 K and 79.4 K shows absence of LRO. Time dependence of thermo-remanent magnetization M TRM(t) studies below 9 K reveal weakening of the inter-cluster interaction with increase in temperature. A summary of these results is that in Zn0.8Cu0.2FeMnO4, ferromagnetic clusters interact antiferromagnetically without LRO but producing a cluster SG state at T SG(0) = 46.6 K, followed by SL behavior below 9 K.