# Thermodynamic, Electromagnetic, and Lattice Properties of Antiperovskite Mn3SbN

Authors: Ying Sun; Yan-Feng Guo; Yoshihiro Tsujimoto; Xia Wang; Jun Li; Clastin I. Sathish; Cong Wang; Kazunari Yamaura
Journal: Advances in Condensed Matter Physics
 (2013)

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## Abstract

The physical properties of polycrystalline Mn3SbN were investigated using measurements of the magnetic, calorimetric, and electronic transport properties. At room temperature, the phase crystallizes in a tetragonal structure with P4/mmm symmetry. A remarkably sharp peak in the heat capacity versus temperature curve was found near 353 K. The peak reaches 723 J mol−1 K−1 at its highest, which corresponds to a transition entropy of 10.2 J mol−1 K−1. The majority of the large entropy change appears to be due to lattice distortion from the high-temperature cubic structure to the room-temperature tetragonal structure and the accompanying Ferrimagnetic transition.


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## Body

## 1. Introduction

Antiperovskite compounds with the formula Mn3XN or Mn3XC (X = Cu, Zn, Ga, Cu, In, or Sn) were discovered in the middle of the last century [1]. Recently, interest in these materials has intensively renewed owing to discoveries of new, potentially useful properties [2–4] such as the giant magnetoresistance of Mn3GaC [5], negative thermal expansion (NTE) of Mn3Cu(Ge)N [6] and Mn3Zn(Ge)N [7], magnetostriction of Mn3CuN [8] and Mn3SbN [9], and near-zero temperature coefficient of the resistivity of Mn3CuN [10] and Mn3NiN [11]. Specifically, Takenaka and Takagi found that Ge-doped Mn3CuN compound has a large NTE (NTE parameter = −25 × 10−6 K−1) [12]; using neutron diffraction, the broad NTE was determined to be associated with the local T4 structure [6]. Asano et al. discovered large magnetostriction in tetragonal Mn3CuN; it expands 0.2% and shrinks 0.1% in the directions parallel and perpendicular to an external 90 kOe magnetic field, respectively [8]. In previous studies, we found a peculiar phase separation and accompanying anomaly in the electronic transport properties of Mn3ZnN [13, 14], while further study indicated that the thermal expansion properties of Mn3ZnN can be controlled by introducing Zn vacancies [15]. In addition, Song et al. observed a canonical spin-glass state in Mn3GaN below the spin-freezing temperature of 133 K [16]. Lukashev et al. systematically studied the spin density of the spin-frustrated state of a Mn-based antiperovskite under mechanical stress [17].The above-mentioned properties enable a variety of potential applications for this type of material. Although the prospective industrial markets are expected to be large and much effort has already been devoted to studying their structural, electromagnetic, and transport properties, further investigations on antiperovskite materials are still required. In this study, the thermodynamic, electromagnetic, and electronic transport properties of Mn3SbN are investigated. In particular, we focused on the notable transition entropy that accompanies the magnetic and crystal structure transition above room temperature.


## 2. Experimental Details

A polycrystalline Mn3SbN sample was prepared via the solid-state reaction of fine powders of Sb (99.99%, Rare Metallic Co.) and Mn2N, which was synthesized by firing Mn powder (99.99%, Sigma Aldrich Co.) in nitrogen at 800°C for 60 h. Stoichiometric amounts of the starting materials were thoroughly mixed, and the mixture was pressed into a pellet. The pellet was sealed in an evacuated quartz tube, heated in a box furnace at 800°C for three days, and then slowly cooled to room temperature in the furnace.The crystal structure of Mn3SbN was analyzed by synchrotron X-ray diffraction (SXRD) using a large Debye-Scherrer camera at the BL15XU NIMS beam line of the SPring-8 facility in Hyogo, Japan. The SXRD data were collected for 2θ ranging from 2° to 60° at intervals of 0.003°. The incident beam was monochromatized at λ=0.65297 Å. The evolution of the Mn3SbN crystal structure with temperature was also determined via the measurement of the SXRD patterns.The temperature dependence of magnetization was measured between 2 and 400 K with applied magnetic fields of 0.1 and 5 kOe using a Magnetic Property Measurements System (Quantum Design). The measurements were conducted on loosely gathered powder under both zero-field cooling (ZFC) and field cooling (FC) conditions. The isothermal magnetization curve was recorded at 10 K between −50 and 50 kOe.Specific heat (Cp) values were measured between 2 and 400 K with cooling using a Physical Properties Measurement System (Quantum Design). The sample was fixed on a stage using a small amount of grease; the heat capacity of the grease was measured first and subtracted from the total Cp.The electrical resistivity (ρ) was measured between 2 and 400 K with cooling and heating using a conventional four-probe techniques with the same apparatus. The AC gauge current and frequency were 10 mA and 30 Hz, respectively. The electrical contacts were prepared on the surface of a bar-shaped piece of the pellet using silver paste and Pt wires.


## 3. Results and Discussion

As shown in Figure1, the synchrotron XRD pattern at room temperature fit well with a model pattern of the proposed structure (space group: P4/mmm). The structural parameters of Mn3SbN were refined by the Rietveld method using the RIETAN-FP program [18]. The occupancy factors of Sb, N, Mn1, and Mn2 were refined to be 1 (fixed), 1 (fixed), 0.97(1), and 0.99(1), respectively, while the isotropic atomic displacement parameters were 0.42(1), 0.84(5), 0.86(1), and 0.78(1) Å2, respectively. The lattice constants were calculated to be a = b = 4.17994(4) Å and c = 4.27718(5) Å. The final Rwp and Rp reliability indexes were below 5.56% and 4.09%, respectively. The analysis revealed 1.91 mass% MnO in the sample as an impurity; as shown later, the magnetic, Cp, and ρ measurements suggest that the impurity does not significantly impact the measurements of Mn3SbN in this study.Figure 1
Rietveld refinement of the synchrotron XRD pattern of Mn3SbN. The crosses and solid lines represent the observed and calculated profiles, respectively, and the difference between the curves is shown at the bottom. Bragg positions are marked by small ticks (upper: Mn3ZnN, lower: MnO).Figure2 displays the temperature dependence of magnetization of polycrystalline Mn3SbN. The magnetization steeply increases upon cooling to around 353 K, which suggests the establishment of long-range magnetic order at the magnetic transition temperature (Tc). In addition, a small hysteresis can be observed between the heating and cooling process, implying the first-order character of the magnetic transition. The remarkable bifurcation between the ZFC and FC curves may originate from the spontaneous alignment of random magnetic Mn moments in domain boundaries. It is worth noting that the hysteresis is less significant at a higher magnetic field of 5 kOe, which supports the domain picture.Figure 2
Temperature dependence of magnetization in magnetic fields of 0.1 and 5 kOe. The left and right insets show the isothermal magnetization curve at 10 K andχ-1 versus T plot of the FC data at 0.1 kOe, respectively.To further study the magnetic properties, we applied the Curie-Weiss law to the paramagnetic portion. As shown in the right inset of Figure2, the χ-1-T plot is well represented by the Curie-Weiss law, that is, the spin-only expression for magnetic susceptibility: χ(T)=C/(T-ΘW), where C is the Curie constant and ΘW is the Weiss temperature. The value of ΘW was determined to be 354 K, which suggests that ferromagnetic correlation is dominant in the spin system. The effective Bohr magneton (μeff) was estimated to be 1.28 μB/Mn from μeff=2.83(C/η)0.5μB, where η is the number of magnetic atoms in the molecular formula (η=3 in the present case). The value of μeff is much lower than that of other antiperovskite manganese nitrides (e.g., 2.87 μB for Mn3ZnN [14]) and even lower than the expected moment for localized S=1/2 spins, suggesting an itinerant character of the 3d electrons in Mn3SbN.From the isothermal magnetization curve (see the inset of Figure2), it was found that the magnetization at 50 kOe is ~0.35 μB/Mn, which is too small to be caused by full ferromagnetic order. The gap suggests that the spins of the Mn atoms are possibly Ferrimagnetically ordered. This Ferrimagnetic interaction is also suggested by the magnetization characteristics above 10 kOe, that is, the magnetization continuously increases with increasing magnetic field without approaching saturation. The Ferrimagnetic order of a related Mn-based antiperovskite compound was explained by a Γ4g spin structure, where two of the three Mn magnetic moments are antiferromagnetically coupled and the third exhibits FM behavior [19]. It is possible that a similar magnetic structure is established in Mn3SbN below 353 K.To further characterize the magnetic transition, the specific heat was measured from 400 to 2 K. As shown in Figure3, the temperature dependence of Cp features a sharp and narrow peak around Tc (ΔCp/R = 87 and ΔT = 3 K, where R is the ideal gas constant). This is indicative of a first-order-like transition, as discussed in [20].Figure 3
Temperature dependence of theCp of Mn3SbN. The left and right insets show a linear fit to the Cp/Tversus T2 curve and an estimation of ΔS, respectively.An estimation of entropy change is essential to understanding the nature of the transition of Mn3SbN. The peak was roughly separated from the baseline using a polynomial function. Analysis indicates that the total transition entropy (ΔS) is ~1.23R (10.2 J/mol K). Since the total entropy change comprises all contributions, including the lattice, electronic, and magnetic changes [20], we evaluated each contribution independently.For the present compound, the abrupt change of the magnetization atTc may induce a large ∂M/∂T; therefore, a large magnetic entropy change (ΔSm) is expected. A series of magnetization curves with small temperature steps were measured; the data allow for a rough estimation of the magnetic entropy change via the thermodynamic Maxwell relation, as follows [21]:
(1)(∂S(T,H)∂H)T=-(∂M(T,H)∂T)H.
The magnetic entropy change, ΔSm(T,H), can be calculated by
(2)ΔSm(T,H)=Sm(T,H)-Sm(T,0)=∫0H(∂M(T,H)∂T)HdH.
The temperature dependence of ΔSm calculated from (2) with fields of 10, 20, 30, 40, and 50 kOe is shown in Figure 4. The ΔSm is maximized around Tc, and the maximum is estimated to be ~2.1 J mol−1 K−1, which implies that the lattice and electronic changes provide a fairly large contribution to the total entropy change.Figure 4
Temperature dependence of the magnetic entropy change when the magnetic field changes from 0 to 10, 20, 30, 40, and 50 kOe, respectively.To investigate the electronic contribution (i.e., the Sommerfeld coefficient orγ), the Cp/T versus T2 plot below 10 K was analyzed by applying the approximate Debye model, as follows:C(T)/T = γ + 2.4π4nN0kB(1/ΘD3)T2 (T≪ΘD,), where n denotes the number of atoms per formula unit, kB is the Boltzmann constant, N0 is the Avogadro constant, and ΘD is the Debye temperature. Fitting to the linear part of the Cp/T versus T2 plot using the least-squares method yielded γ and ΘD values of ~7.03(1) mJ mol−1 K−2 and 326(2) K, respectively. Compared with the parameters determined for other antiperovskite nitrides, Mn3SbN has a much lower γ, which indicates that the electronic correlation is somewhat weakened [20]. Thus, the electronic contribution might not be a dominant contributor to the total transition entropy.In addition to the magnetic and electronic contributions, a possible lattice change may need to be investigated to analyze the total transition entropy. The variation of the synchrotron XRD pattern with temperature was measured. As shown in Figure5(b). It can be seen that some typical reflections disappear with temperature, for example, the two reflections (002) and (200) for the P4/mmm lattice merge to one reflection. By the Rietveld analysis of the synchrotron XRD patterns, the structural change from tetragonal to cubic was defined, and the lattice constants were determined as a function of temperature, as shown in Figure 5(a). It is obvious that lattice parameter c increases slightly with increasing temperature, whereas a gradually decreases. When the temperature crosses Tc, the tetragonal structure completely transforms to an unidentified cubic structure. Hence, the lattice distortion must contribute to the total entropy change.Variation in (a) lattice parameters and (b) synchrotron XRD patterns with temperature for Mn3SbN.
(a)
(b)According to the thermodynamic relation, the magnetization (M) is equal to the first derivative of the magnetic free energy by the magnetic field, that is, df(M)/dH [22]. Therefore, the sharp transition indicates that the energy barrier in the free energy that separates the paramagnetic and ferromagnetic states is large. Accordingly, Tc and the energy barrier height probably correlate with the electronic density of states, which exhibits a sharp peak near the Fermi level [23]; therefore, the large entropy change is possibly related to the reconstruction of the electronic structure, which could induce the magnetic and structural transition. Since such an electronic reconstruction is often sharply reflected in a ρ-T curve, the electronic transport properties of Mn3SbN were carefully measured (shown in Figure 6). It is evident that an abnormal drop appears at Tc in the ρ-T curve, which is indicative of an electronic structure reconstruction. In addition, as shown in the inset of Figure 6, a small hysteresis was observed between the warming and cooling curves; this is in agreement with a first-order transition.Figure 6
Variation ofρ with temperature for Mn3SbN upon cooling and warming. The inset shows an enlarged view of the ρ variation around the magnetic transition.


## 4. Conclusions

In conclusion, the thermodynamic, electromagnetic, and transport properties of antiperovskite Mn3SbN were studied. The phase crystallizes in a tetragonal structure with a = b = 4.17994(4) Å and c = 4.27718(5) Å at room temperature. The Cp measurements revealed a sharp endothermic peak in the Cp-T curve at 353 K, which corresponds to a large entropy change (~10.2 J mol−1 K−1). The present study clearly indicates that the entropy change is accompanied with a Ferrimagnetic transition and lattice distortion as well as a possible electronic structure reconstruction.



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*Source: 286325-2013-01-10.xml*