Large magnetocaloric effect in the kagome ferromagnet Li$_9$Cr$_3$(P$_2$O$_7$)$_3$(PO$_4$)$_2$

Abstract

Single-crystal growth, magnetic properties, and magnetocaloric effect of the $S = 3/2$ kagome ferromagnet Li$_9$Cr$_3$(P$_2$O$_7$)$_3$(PO$_4$)$_2$ (trigonal, space group: $P\bar{3}c1$) are reported. Magnetization data suggest dominant ferromagnetic intra-plane coupling with a weak anisotropy and the onset of ferromagnetic ordering at $T_{\rm C} \simeq 2.6$ K. Microscopic analysis reveals a very small ratio of interlayer to intralayer ferromagnetic couplings ($J_{\perp}/J \simeq 0.02$). Electron spin resonance data suggest the presence of short-range correlations above $T_{\rm C}$ and confirms quasi-two-dimensional character of the spin system. A large magnetocaloric effect characterized by isothermal entropy change of $-\Delta S_{\rm m}\simeq 31$ J kg$^{-1}$ K$^{-1}$ and adiabatic temperature change of $-\Delta T_{\rm ad}\simeq 9$ K upon a field sweep of 7 T is observed around $T_{\rm C}$. This leads to a large relative cooling power of $RCP \simeq 284$ J kg$^{-1}$. The large magnetocaloric effect, together with negligible hysteresis render Li$_9$Cr$_3$(P$_2$O$_7$)$_3$(PO$_4$)$_2$ a promising material for magnetic refrigeration at low temperatures. The magnetocrystalline anisotropy constant $K \simeq -7.42 \times 10^4$ erg cm$^{-3}$ implies that the compound is an easy-plane type ferromagnet with the hard axis normal to the $ab$-plane, consistent with the magnetization data.