Antiferromagnetism, spin-glass state, H-T phase diagram, and inverse magnetocaloric effect in Co2RuO4

Static and dynamic magnetic properties of normal spinel Co2RuO4= (Co2+)A[Co3+Ru3+](B)O-4 are reported based on our investigations of the temperature (T), magnetic field (H) and frequency (f) dependence of the ac-magnetic susceptibilities and dc-magnetization (M) covering the temperature rangeT= 2 K-400 K and H up to 90 kOe. These investigations show that Co2RuO4 exhibits an antiferromagnetic (AFM) transition at T-N similar to 15.2 K, along with a spin-glass state at slightly lower temperature (T-SG) near 14.2 K. It is argued thatT(N)is mainly governed by the ordering of the spins of Co2+ ions occupying theA-site, whereas the exchange interaction between the Co2+ ions on theA-site and randomly distributed Ru(3+)on theB-site triggers the spin-glass phase, Co3+ ions on theB-site being in the low-spin non-magnetic state. Analysis of measurements ofM(H,T) for T<T-N are used to construct theH-Tphase diagram showing thatT(SG)shifts to lowerTvarying as H-2/3.2 expected for spin-glass state whereasT(N)is nearlyH-independent. ForT>T-N, analysis of the paramagnetic susceptibility (chi) vs.Tdata are fit to the modified Curie-Weiss law,chi=chi(0)+C/(T+theta), with chi(0)= 0.0015 emu mol(-1)Oe(-1)yielding theta= 53 K andC= 2.16 emu-K mol(-1)Oe(-1), the later yielding an effective magnetic moment mu(eff)= 4.16 mu(B)comparable to the expected value of mu(eff)= 4.24 mu(B)per Co2RuO4. Using T-N,theta and high temperature series for chi, dominant exchange constant J(1)/k(B)similar to 6 K between the Co(2+)on theA-sites is estimated. Analysis of the ac magnetic susceptibilities near T-SG yields the dynamical critical exponent z nu= 5.2 and microscopic spin relaxation time tau(0)similar to 1.16 x 10(-10)sec characteristic of cluster spin-glasses and the observed time-dependence ofM(t) is supportive of the spin-glass state. LargeM-Hloop asymmetry at low temperatures with giant exchange bias effect (H-EB similar to 1.8 kOe) and coercivity (H-C similar to 7 kOe) for a field cooled sample further support the mixed magnetic phase nature of this interesting spinel. The negative magnetocaloric effect observed belowT(N)is interpreted to be due to the AFM and SG ordering. It is argued that the observed change from positive MCE (magnetocaloric effect) forT>T(N)to inverse MCE forT<T(N)observed in Co2RuO4(and reported previously in other systems also) is related to the change in sign of ( partial derivative M/partial derivative T) vs. T data.