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

Spinels (AB(2)O(4)) 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 (Zn-0.8(2+) Cu-0.2(2+)) A [Fe-0.4(2+) Fe-0.6(3+) Mn3+](B)O4-delta. Analysis of the temperature dependence of magnetization (M), ac magnetic susceptibilities (chi' and chi''), dc susceptibility (chi), heat capacity C-p, and neutron diffraction (ND) measurements show complex temperature-dependent short-range order (SRO) but without LRO. The data of chi vs. T fits the Curie-Weiss law: chi = C/(T - theta) from T = 250 K to 400 K with theta similar or equal to 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 mu(eff) = 5.13 mu 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+down arrow)(A)[Fe2+down arrow, Fe3+down arrow, Mn3+down arrow](B) leading to FM clusters interact antiferromagnetically at low temperatures. Temperature dependence of d(chi T)/ dT shows the onset of ferrimagnetism below similar to 100 K and peaks near 47 K and 24 K. The relaxation time t obtained from temperature and frequency dependence of chi'' 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 T-SG (H) follows the equation: T-SG (H) = T-SG (0) [ 1- AH(2/phi)] with T-SG (0) = 46.6 K, A = 8.6 x 10(-3) Oe(-0.593) and phi = 3.37. The temperature dependence of hysteresis loops yields coercivity H-C similar to 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 C-p 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 T-2; 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 MTRM(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.