† Corresponding author. E-mail:
Project supported by the National Natural Science Foundation of China (Grant Nos. 51371193 and 11534015), the Youth Innovation Promotion of the Chinese Academy of Sciences (Grant No. 2013004), and the Science Fund from the Chinese Academy of Sciences (Grant Nos. XDB07030200 and KJZD-EW-M05).
We present a study of magnetocaloric effect of the quasi-two-dimensional (2D) ferromagnet (CH3NH3)2CuCl4 in ab plane (easy-plane). From the measurements of magnetic field dependence of magnetization at various temperatures, we have discovered a large magnetic entropy change associated with the ferromagnetic–paramagnetic transition. The heat capacity measurements reveal an abnormal adiabatic change below the Curie temperature Tc ~ 8.9 K, which is caused by the nature of quasi-2D layered crystal structure. These results suggest that perovskite organic–inorganic hybrids with a layered structure are suitable candidates as working substances in magnetic refrigeration technology.
The magnetocaloric effect (MCE) is the reversible entropy or temperature change of a magnetic material upon the change of external magnetic field.[1–4] Most of the focus is on achieving high performance with giant magnetic cooling power on rigid inorganic materials. To realize the commercial magnetic refrigerators, vast improvements have been gone through in the search for new magnetic materials in terms of large MCE and relative cooling capacity. A giant MCE has been exhibited in the rigid inorganic materials with three-dimensional (3D) crystal structure such as pseudobinary alloys containing rare earth Gd5(Si2Ge2), La(FexSi1 − x)13, perovskite oxides, sulfide spinels, hexaferrites, etc.[5–12]
During recent decades, the versatility of the organic–inorganic hybrid materials has led to a huge expansion of the organic electronics.[13–21] In particular, the organic–inorganic hybrid halide perovskite materials have attracted intense attention due to the extraordinary photonic and electronic properties.[15–18] However, their potential of caloric effect originating from the ferroelectricity or magnetism has never been noticed, such as (CH3NH3)PbI3,[16–18] (CnH2n + 1NH3)2MCl4 (M = Mn, Fe, Cu; n = 1,2,3,…),[19–21] etc. To reveal the multifunctional performance of organic–inorganic hybrid materials and realize their large-scale application eventually, in this paper, the fundamental study on MCE in a prototype organic–inorganic hybrid with two-dimensional (2D) or quasi-2D structure is presented in (CH3NH3)2CuCl4 (MA2CuCl4).
The compound MA2CuCl4 crystallizes in the layered perovskite structure, consisting of staggered layers of corner-sharing CuCl6 octahedra interleaved by alkylammonium cations (CH3NH3)+, as illustrated in Fig.
Single crystals of MA2CuCl4 are naturally grown layer-by-layer along [001] direction by a solvothermal condition method. Yellow plate single crystals with a maximum size of 5 mm × 5 mm × 0.35 mm are obtained. Powder x-ray diffraction patterns with CuKα radiation revealed the single phase monoclinic perovskite structure with P21/a, which is in agreement with literature.[27] The magnetization measurements were performed with a superconducting quantum interference device magnetometer (Quantum Design MPMS) with the magnetic field (B) applied parallel to the metal-halogen layers. The heat capacity was measured under the applied B of 0, 2, and 5 T using a physical property measurement system (Quantum Design).
Figure
Isothermal magnetization curves were recorded in the temperature range of 5 K–30 K in the magnetic field up to 5 T [Fig.
From the thermodynamical theory, the entropy change generated by the variation of the magnetic field from 0 to Hmax is given by
The entropy changes associated with magnetic field variations have been calculated with Eq. (
Based on Eq. (
The large magnetic entropy change in MA2CuCl4 must have originated from the considerable increase of magnetization or Tc with magnetic fields. With the observation of a large magnetic entropy change and the increasing ΔTad in low temperature, one can conclude that a strong spin-lattice coupling in the magnetic ordering process and quasi-2D crystal structure would lead to magnetic entropy change near Tc and favors the MCE effect.
Though the maximum of entropy change is smaller than the most conspicuous magnetocaloric materials, MA2CuCl4 single crystalline and its derivatives are easy to be synthesized at room temperature and exhibits layered structure as well as potential multicaloric effect that is beneficial for the application in cryogen technique and alternative stimulus.[20,30,31] Besides, since the Curie temperature of organic–inorganic hybrids is easy to modify by the replacement of organic functional group, a large magnetic entropy change may be tuned from low temperature to near room temperature, which is meritful for operating magnetic refrigeration at various temperatures.[30]
In conclusion, MA2CuCl4 shows a large MCE with its second-order magnetic transition. The results obtained show a large magnetic entropy change near the ferromagnetic–paramagnetic transition and an increasing adiabatic temperature change below Tc. The large magnetocaloric effect in MA2CuCl4 suggests that organic–inorganic hybrid is a suitable candidate as working substance in magnetic refrigeration technology because of (i) large magnetic entropy change, (ii) soft magnetism and reversible MCE, (iii) wide temperature span of ΔSH and large RCP, (iv) easy to fabricate and tune the magnetic transition temperature by modifying the organic functional group, and (v) potentially multicaloric effect to enhance the MCE.
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