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The effects of sintering temperature (Ts) and chemical substitution on the structural and magnetic properties of manganite compounds La1-xSrxMn1-yFeyO3 (0.025 <= x <= 0.7; y= 0.01,0.15) are explored in a search to optimize their magnetocaloric properties around room temperature. A ferromagnetic (FM) to paramagnetic (PM) phase transition is observed at a Curie temperature Tc that can be controlled to approach room temperature by Sr and Fe substitution, but also by adjusting the sintering temperature Ts. Accordingly, the magnetic entropy change (-DSM) quantifying the magnetocaloric effect (MCE) presents a peak at or close to Tc that shifts and broadens with both Sr and Fe doping and is further tuned with sintering temperature. Altogether, we show that it is possible to adjust the strength and dominance of the ferromagnetic coupling in these ceramics, but also using disorder as a tool to broaden and adjust the temperature range with significant magnetic entropy change., Comment: 61 pages, 14 figures, 3 tables. Supp. mat. : 3 figures, 1 table. Submitted to J. Magn. Magn. Mater

In this paper, we report on the magnetic and magnetocaloric features of Dy-substituted YMn$_2$O$_5$ (Y$_{1-x}$Dy$_x$Mn$_2$O$_5$) with $x=$ 0.6, 0.8, and 1 series elaborated by sol-gel method. X-ray diffraction and Raman measurements attest well the high quality of our polycrystalline samples that crystallize in an orthorhombic structure with the Pbam space group. The Raman phonon frequencies were carried out and compared with the lattice dynamics calculations to identify the vibrational properties of all detected modes at room temperature. As expected, our magnetic study reveals that the magnetization was enhanced by the substitution of Y$^{3+}$ by Dy$^{3+}$. The Dy-substituted YMn$_2$O$_5$ sets the N\'eel transition [TN (Mn)] in the temperature range going from 40 to 45 K favoring the emergence of a transition at a very low temperature due to the long-range ordering of the Dy3+ magnetic moments below 13K [TN (Dy)]. Dual peaks in the magnetic entropy change curve are also observed being in good agreement with magnetization data, which enlarges the range of application of these materials. On the other hand, a large magnetocaloric effect is observed close to 13 K which is mainly due the ordering of Dy$^{3+}$ magnetic moments. Also, the incommensurate antiferromagnetic transition of Mn magnetic moment taking place around 40 K affects slightly the entropy change. Our refrigerant capacity (RC) findings are higher compared to the average of RC for a, b, c axis of single crystal samples as HoMn$_2$O$_5$ and TbMn$_2$O$_5$, which confirms that our polycrystalline materials stand for promising magnetic refrigerant candidates that can be invested in space technology, hydrogen and helium liquefaction at cryogenic temperature.

Combining multiple degrees of freedom in strongly-correlated materials such as transition-metal oxides would lead to fascinating magnetic and magnetocaloric features. Herein, the strain effects are used to markedly tailor the magnetic and magnetocaloric properties of PrVO3 thin films. The selection of appropriate thickness and substrate enables us to dramatically decrease the coercive magnetic field from 2.4 T previously observed in sintered PVO3 bulk to 0.05 T for compressive thin films making from the PrVO3 compound a nearly soft magnet. This is associated with a marked enhancement of the magnetic moment and the magnetocaloric effect that reach unusual maximum values of roughly 4.86 uB and 56.8 J/kg K in the magnetic field change of 6 T applied in the sample plane at the cryogenic temperature range (3 K), respectively. This work strongly suggests that taking advantage of different degrees of freedom and the exploitation of multiple instabilities in a nanoscale regime is a promising strategy for unveiling unexpected phases accompanied by a large magnetocaloric effect in oxides., Comment: This paper is accepted for publication in Applied Physics Letters

In this paper, we mainly focus on the magnetic and magnetocaloric features of La2-xDyxNiMnO6 double perovskites. Their magnetocaloric properties are investigated in terms of both entropy and adiabatic temperature changes. In contrast to early works, it was found that the Dy2NiMnO6 compound unveils dominant antiferromagnetic interactions under very low magnetic fields. The ordering of its Dy3+ magnetic moments is associated with a giant magnetocaloric effect at very low temperatures, while the established ferromagnetic Ni-O-Mn super-exchange interactions close to 100 K give rise to a moderate magnetocaloric level, only. On the other hand, the doping of Dy2NiMnO6 with high amounts of large-size rare earth elements such as La would enable us to cover an unusually wide magnetocaloric temperature range going from the liquid helium temperature up to room-temperature. More interestingly, the presence of both ordered and disordered ferromagnetic phases in La1.5Dy0.5NiMnO6 maintains constant the isothermal entropy changes over a temperature span of about 200 K, being a favorable situation from a practical point of view., Comment: Accepted for publication in Journal of Physics: D, 2019

It is known that orthorhombic RMnO3 multiferroics (R = magnetic rare earth) with low symmetry exhibit a large rotating magnetocaloric effect because of their strong magnetocrystalline anisotropy. In this paper, we demonstrate that the hexagonal ErMnO3 single crystals also unveils a giant rotating magnetocaloric effect that can be obtained by spinning them in constant magnetic fields around their a or b axes. When the ErMnO3 crystal is rotated with the magnetic field initially parallel to the c-axis, the resulting entropy change reaches maximum values of 7, 17 and 20 J/kg K under a constant magnetic field of 2, 5 and 7 T, respectively. These values are comparable or even larger than those shown by some of the best orthorhombic phases. More interestingly, the generated anisotropic thermal effect is about three times larger than that exhibited by the hexagonal HoMnO3 single crystal. The enhancement of the rotating magnetocaloric effect in the hexagonal ErMnO3 compound arises from the unique features of Er3+ magnetic sublattice. In fact, the Er3+ magnetic moments located at 2a sites experience a first-order metamagnetic transition close to 3 K along the c-axis resulting in a peaked magnetocaloric effect over a narrower temperature range. In contrast, the (paramagnetic) behaviour of Er3+ magnetic moments within the ab-plane, produces a larger magnetocaloric effect over a wider temperature range. Therefore, the magnetocaloric effect anisotropy is maximized between the c and the ab-directions, leading to a giant rotating magnetocaloric effect., Comment: Accepted for publication in Physical Review B, 2018

In previous studies, we have reported that double perovskite La2NiMnO6 presents a non-negligible potential for room temperature magnetocaloric tasks. With the aim of improving even further the cooling performances and the working temperature range of double perovskites, we report the magnetic and magnetocaloric properties of La2MnFeO6 and ALaMnFeO6 (A = Sr, Ba, Ca) compounds. X-ray diffraction (XRD) and Rietveld refinement show that La2MnFeO6 (LMFO) and CaLaMnFeO6 (CLMFO) samples crystallize in an orthorhombic structure with the Pnma space group. However, a rhombohedral structure with the R3C space group is obtained for BaLaMnFeO6 (BLMFO) and SrLaMnFeO6 (SLMFO) samples. Substituting La by Ba or Sr in LMFO leads to a clear increase of the Curie temperature (Tc) compared to LMFO from 150 K for BLMFO up to 350 K for SLMFO. Moreover, CLMFO shows the smallest Tc down to 70 K. Ferromagnetic-like behavior is observed for SLMFO and BLMFO while CLMFO's magnetism resembles that of LMFO. A clear connection between the structural parameters and the magnetic properties of these doped LMFO samples is unveiled as the highest Tc and the largest magnetization are observed for SLMFO which shows also bond angles closest to 180{\deg} and the smallest bond lengths, thus optimizing the superexchange interaction. The partial substitution of Sr for La leads in fact to a significant magnetocaloric effect over a wide operating temperature range extending beyond 300 K. For some optimal growth conditions, its entropy change varies slowly over an unusually large temperature range, which is of clear interest from a practical point of view., Comment: 35 pages including Supplemental materials, 17 figures. New version with additional data and extended analysis

Raman and infrared spectroscopies are used as local probes to study the dynamics of the Nd-O bonds in the weakly multiferroic NdMn2O5 system. The temperature dependence of selected Raman excitations reveals the splitting of the Nd-O bonds in NdMn2O5. The Nd3+ ion crystal field (CF) excitations in NdMn2O5 single crystals are studied by infrared transmission as a function of temperature, in the 1800-8000 cm-1 range, and under an applied magnetic field up to 11 T. The frequencies of all 4Ij crystal-field levels of Nd3+ are determined. We find that the degeneracy of the ground-state Kramers doublet is lifted ({\Delta}0 ~7.5 cm-1) due to the Nd3+-Mn3+ interaction in the ferroelectric phase, below TC ~ 28 K. The Nd3+ magnetic moment mNd(T) and its contribution to the magnetic susceptibility and the specific heat are evaluated from {\Delta}0(T) indicating that the Nd3+ ions are involved in the magnetic and the ferroelectric ordering observed below ~ 28 K. The Zeeman splitting of the excited crystal field levels of the Nd3+ ions at low temperature is also analyzed., Comment: This paper is accepted for publication as a Regular Article in Physical Review B

The search for room-temperature magnetocaloric materials for refrigeration has led to investigations of double perovskites. In particular, a puzzle has appeared in the La$_2$MnNiO$_6$, La$_2$MnCoO$_6$ and La$_2$MnFeO$_6$ family of compounds. They share the same crystal structure, but while La$_2$MnNiO$_6$ and La$_2$MnCoO$_6$ are ferromagnets below room temperature, La$_2$MnFeO$_6$, contrary to simple expectations, is a ferrimagnet. To solve this puzzle, we use density-functional theory calculations to investigate the electronic structure and magnetic exchange interactions of the ordered double perovskites. Our study reveals the critical role played by local electron-electron interaction in the Fe-$d$ orbital to promote the Fe$^{3+}$ valence state with half-filled $d$-shell over Fe$^{2+}$ and to establish a ferrimagnetic ground state for La$_2$MnFeO$_6$. The importance of Hund's coupling and Jahn-Teller distortion on the Mn$^{4+}$ ion is also pointed out. Exchange constants are extracted by comparing different magnetically ordered states. Mean-field and classical Monte-Carlo calculations on the resulting model give trends in $T_C$ that are in agreement with experiments on this family of materials., Comment: accepted in Physics. Rev. B

We report on the magnetic and magnetocaloric properties of a MnRhAs single crystal. The ternary arsenide exhibits a rather complex magnetic behaviour. A first order metamagnetic type transition from antiferromagnetic (AFI) to ferromagnetic (F) states takes place at Tt ~ 158 K, and a second order transition from ferromagnetic (F) to antiferromagnetic (AFII) states occurs at TC ~196 K, the paramagnetic state occurring at T > TN = 238 K. Magnetic entropy changes were calculated using, Maxwell relation and Clausius-Clapeyron equation. Both approaches are compared and discussed. The AFI-F transition in MnRhAs gives rise to an interestingly high level of negative magnetocaloric effect. Under a field change 0-1 T, the maximum magnetic entropy variation is about 3 J/kg K. For sufficiently high enough magnetic fields, the magnetocaloric working temperature range below 158 K can be covered. The F-AFII transition is accompanied by a relatively modest MCE (-2.3 J/kg K for 5 T at TC = 196 K), but it improves the working temperature span as well as the magnetocaloric properties. A minimum estimated refrigerant capacity of about 900 J/kg can be provided by a MnRhAs single crystal compound

In this paper, we report on the magnetocaloric properties of some selected multiferroic oxides, namely HoMn2O5 and La2(Ni,Co)MnO6 compounds which exhibit transition points from 10K up to almost room temperature. In order to avoid grain boundary effects and structural inhomogeneity observed frequently in polycrystalline samples, only single crystals were considered for this study., Comment: 6th IIF-IIR International Conference on Magnetic Refrigeration Victoria, BC, 7-10 September 2014

Solid state-refrigerants have generated worldwide interest owing to their growing potential for use in efficient and green cooling devices. Caloric effects could be obtained by manipulating their degrees of freedom such as magnetization, electric polarization and volume using a variable external field. In conventional magnetocaloric refrigeration systems, the magnetocaloric effect is exploited by moving the active material in and out of the magnetic field source. Here we demonstrate that a giant and reversible magnetocaloric effect can be generated simply by rotating the multiferroic TbMn2O5 single crystal around its b axis in a relatively low constant magnetic field applied in the ac plane. For a magnetic field applied along the easy axis a, we report an entropy change of 12.25 J/kg K at about 10 K in a field change of 5 T which is 100 times larger than that found when the field is applied along the hard axis c. When the TbMn2O5 is rotated with the field remaining in the ac plane, the associated adiabatic temperature change reaches minimum values of 8 K and 14 K under 2 T and 5 T, respectively. This giant rotating magnetocaloric effect in TbMn2O5 is caused by the colossal anisotropy of the entropy change, the enhancement of the magnetization under relatively moderate magnetic fields and the lower magnitude of specific heat. On the other hand, the application of the coherent rotational model demonstrates that the rotating magnetocaloric effect exhibited by TbMn2O5 does not originate directly from the magneto-crystalline anisotropy. Our results should inspire and open new ways toward the implementation of compact, efficient and embedded magnetocaloric devices for low temperature and space application. Its potential operating temperature range of 2 to 30 K makes it a great candidate for the liquefaction of hydrogen., Comment: The short version of this paper is published in Applied Physics Letters [Appl. Phys. Lett. 108, 102401 (2016)]