Synthesis, Crystal Structure, Resistivity, Magnetic, and Theoretical

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Synthesis, Crystal Structure, Resistivity, Magnetic, and Theoretical Study of ScUS3 Jai Prakash,† Adel Mesbah,†,‡ Matthew D. Ward,† Sébastien Lebègue,§ Christos D. Malliakas,† Minseong Lee,⊥ Eun Sang Choi,⊥ and James A. Ibers*,† †

Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States ICSM, UMR 5257 CEA/CNRS/UM2/ENSCM, Site de Marcoule - Bât. 426, BP 17171, 30207 Bagnols-sur-Cèze cedex, France § Laboratoire de Cristallographie, Résonance Magnétique et Modélisations (CRM2, UMR CNRS 7036),Institut Jean Barriol, Université de Lorraine, BP 239, Boulevard des Aiguillettes, 54506 Vandoeuvre-lès-Nancy, France ⊥ Department of Physics and National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310-3706, United States ‡

S Supporting Information *

ABSTRACT: Single crystals of ScUS3 were synthesized in high yield in a single step at 1173 K. ScUS3 crystallizes in the FeUS3 structure type in the space group D17 2h−Cmcm of the orthorhombic system with four formula units in a cell of dimensions a = 3.7500(8) Å, b = 12.110(2) Å, and c = 9.180(2) Å. Its structure consists of edge- and corner-sharing ScS6 octahedra that form two-dimensional layers. U atoms between layers are connected to eight S atoms in a bicapped trigonal-prismatic fashion. ScUS3 can be easily charge-balanced as Sc3+U3+(S2−)3 as there are no S−S single bonds present in the crystal structure. High temperature-dependent resistivity measurements on a single crystal of ScUS3 show semiconducting behavior with an activation energy of 0.09(1) eV. A magnetic study on powdered single crystals of ScUS3 reveals an antiferromagnetic transition at 198 K followed by a ferromagnetic transition at 75 K. The weak ferromagnetic behavior at low temperature may originate from canted antiferromagnetic spins. A density functional theory (DFT) calculation predicts ScUS3 to be ferromagnetic and either a very poor metal or a semiconductor with a very small gap.

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INTRODUCTION The vast majority of known uranium chalcogenide compounds contain U4+. Among the few that contain U3+ are ScUS31 and ScU3S6.2 This assignment of U3+ was based on the U−S distances being longer than those in confirmed U4+-containing compounds. Further evidence for these compounds containing U3+ comes from an X-ray absorption near-edge spectroscopy (XANES) study of ScU8S173 that showed that the compound contains Sc3+ and hence that Sc3+/U3+ is favored over Sc2+/U4+ in uranium sulfides. ScUS3 is a member of the large class of AnMQ3 compounds, where An = actinide, M = metal, and Q = S, Se, or Te. Some examples include VUQ3 (Q = S, Se),4 CrUQ3 (Q = S, Se),4 FeUQ3 (Q = S, Se),5,6 CoUQ3 (Q = S,7 Se4), NiUQ3 (Q = S,8 Se4), RuUS3,9 and RhUS3.9 The crystal structures of these compounds are related to those of orthorhombic perovskites and involve MQ6 octahedra and AnQ8 polyhedra. Depending on the nature of the M atoms these compounds crystallize in a three-dimensional structure in space group Pnma10 or, as does ScUS3, in a layered structure in space group Cmcm.1,5 This structure is very simple with a single U atom in the asymmetric unit of the unit cell. As such it is an attractive compound for study of the rare U3+ oxidation state. Although the crystal structure of ScUS3 was established in 19781 no physical © XXXX American Chemical Society

measurements have been made, presumably owing to the stringent experimental conditions involving very high temperatures and H2S required to synthesize this compound. Here we present a straightforward low-temperature high-yield synthesis of ScUS3, its low-temperature crystal structure, and resistivity, magnetic, and density functional theory (DFT) studies.

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EXPERIMENTAL METHODS

Synthesis and Analysis. Caution! Depleted U is an α-emitting radioisotope and as such is considered a health risk. Its use requires appropriate inf rastructure and personnel trained in the handling of radioactive materials. Sc (Aldrich, 99.9%) and S (Mallinckrodt, 99.6%) were used as obtained. Depleted U powder was obtained by hydridization and decomposition of turnings (IBI Laboratories) in a modification11 of a literature method.12 Black needle-shaped crystals of ScUS3 were obtained by reacting stoichiometric amounts of Sc (7.6 mg, 0.169 mmol), U (40 mg, 0.168 mmol), and S (162 mg, 0.505 mmol). The reactants were weighed inside an Ar-filled glovebox and then transferred to a carbon-coated fused-silica tube that was then evacuated to 1 × 10−4 Torr and flame-sealed. The tube was heated to 1173 K in 48 h and annealed for 96 h. The tube was allowed to cool Received: November 3, 2014

A

DOI: 10.1021/ic502656u Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry to 973 K in 96 h and then to 573 K in 192 h. Finally, the tube was cooled to 298 K in 48 h. The slow cooling rates were employed to obtain high-quality crystals. The reaction product contained black needles of ScUS3 and black plates of UOS.13 Energy-dispersive X-ray (EDX) spectroscopic analysis of the needles using a Hitachi 3400 SEM showed the presence of Sc/U/S ≈ 1:1:3. Structure Determination. The crystal structure of ScUS3 was determined from single-crystal X-ray diffraction data collected with the use of graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å) at 100(2) K on a Bruker APEX2 diffractometer.14 The algorithm COSMO implemented in the program APEX2 was used to establish the data collection strategy with a series of 0.3° scans in ω and φ. The exposure time was 15 seconds/frame, and the crystal-to-detector distance was 60 mm. The collection of intensity data as well as cell refinement and data reduction were carried out with the use of the program APEX2.14 Face-indexed absorption, incident beam, and decay corrections were performed with the use of the program SADABS.15 The crystal structure of ScUS3 was solved and refined in a straightforward manner with the use of the SHELX14 program package.15,16 The program STRUCTURE TIDY17 in PLATON18 was used to standardize the atomic positions. Further details are given in Table 1 and in the Supporting Information.

positions were taken to be identical to the experimental ones. The two possible magnetic configurations of the magnetic moments on the U atoms within the cell were calculated, and the one with the lower energy was retained as being the ground state of the system. The default cutoff and a k-point mesh of 8 × 8 × 6 to sample the Brillouin zone were used to reach convergence.

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RESULTS AND DISCUSSION Synthesis. The procedure used in 1978 to obtain crystals of ScUS31 involved the synthesis of a polycrystalline sample of ScUS3 by heating stoichiometric amounts of Sc2O3 and UO2 at 1623 K under flowing H2S gas. The resultant polycrystalline powder of ScUS3 was then melted at 2073 K under Ar to yield single crystals. Although the use of CsCl as a flux frequently leads to successful syntheses of metal chalcogenides, in this instance it produced ScU8S17 instead of the target ScUS3 phase.3 Instead, we synthesized single crystals of ScUS3 in ∼90 wt % yield in a single step by the stoichiometric reaction of the elements at 1173 K. Crystal Structure. ScUS3 crystallizes in the FeUS3 structure type6,8 in the space group D17 2h−Cmcm of the orthorhombic system with four formula units in a cell of dimensions a = 3.7500(8) Å, b = 12.110(2) Å, and c = 9.180(2) Å at 100(2) K (Table 1). The cell constants obtained earlier at 298 K were a = 3.765(2) Å, b = 12.134(6) Å, and c = 9.176(5) Å.1 The asymmetric unit of the crystal structure contains one Sc (site symmetry 2/m), one U (m2m), and two S atoms (S1 (m) and S2 (m2m)). The crystal structure of ScUS3 viewed approximately along the a-axis is shown in Figure 1. The U atoms in

Table 1. Crystallographic Data and Structure Refinement for ScUS3 space group a (Å) b (Å) c (Å) V (Å3) λ (Å) Z T (K) ρ (g cm−3) μ (mm−1) R(F)a Rw(F02)b

D17 2h−Cmcm 3.7500(8) 12.110(2) 9.180(2) 416.89(14) 0.71073 4 100(2) 6.041 41.696 0.025 0.054

R(F) = Σ||F0| − |Fc||/Σ|F0| for F02 > 2σ(F02). bRw(F02) = {Σ[w(F02 − Fc2)2]/ΣwFo4}1/2. For F02 < 0, w−1 = σ2(F02); for F02 ≥ 0, w−1 = σ2(F02) + (0.0220F02)2 a

Resistivity Study. Four-probe temperature-dependent resistivity data on a single crystal of ScUS3 were collected using a homemade resistivity apparatus equipped with a Keithley 2182 nanovoltmeter, a Keithley 236 source measure unit, and a high-temperature vacuum chamber controlled by a K-20 MMR system. An I−V curve from 1 × 10−5 A to −1 × 10−5 A with a step of 2 × 10−6 Å was measured for each temperature point, and resistance was calculated from the slope of the I−V plot. Data acquisition was controlled by custom-written software. Graphite paint (PELCO isopropanol-based graphite paint) was used for electrical contacts with Cu of 0.025 mm thickness (Omega). Direct current was applied along an arbitrary direction. Magnetic Study. Needle-shaped single crystals of ScUS3 were manually separated from the black plates of UOS byproduct. The magnetic property measurements of 5.0 mg of ground single crystals of ScUS3 were made with the use of a Quantum Design MPMS SQUID magnetometer. The sample was mixed with silicone vacuum grease to prevent movement under high magnetic field. The temperaturedependent susceptibility data were obtained under zero field-cooled (ZFC) and field-cooled (FC) conditions at fields of 1 kOe and 10 kOe. Field-dependent magnetization curves were obtained at 5, 10, 20, and 130 K after the sample was cooled from 298 K under zero field. Theoretical Calculations. First-principles calculations were carried out with the Vienna ab Initio Simulation Package (VASP) code,19,20 implementing the projector augmented wave method.21 DFT22,23 at the HSE24−26 level for the exchange-correlation potential was used, including spin polarization. The unit cell and atomic

Figure 1. Crystal structure of ScUS3 viewed nearly along the [100] direction. Here and in succeeding figures Sc is green, U is black, and S is orange.

this structure are coordinated to eight S atoms in a bicapped trigonal-prismatic arrangement (Figure 2). Each U atom shares two S1/S2/S1 triangular faces with neighboring U atoms in the [100] direction, and S1 atoms are shared with three neighboring U atoms. Sc atoms are connected to six S atoms in a slightly distorted octahedral fashion, and these octahedra share S1/S1 edges with neighboring octahedra in the [100] direction and S2 vertices with other octahedra in the [001] direction (Figure 3). This arrangement of ScS6 octahedra forms two-dimensional infinite layers perpendicular to the b-axis; U atoms sit between these layers. B

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those in ScU3S6 (2.822(1) Å to 3.166(1) Å),2 which also contains eight-coordinate U 3+ . As expected, the U−S interatomic distances in ScUS3 are longer than those in related U4+−S compounds (Table 3). The Sc−S distances (2.492(1) Å Table 3. U−S Interatomic Distances in Some Related Compounds Containing US8 Polyhedraa

Figure 2. U network in ScUS3 viewed nearly down the [010] direction.

compound

U oxidation state

U−S distances (Å)

reference

ScUS3 ScU3S6 U3S5 FeUS3 Ba2US6 Rb2Pd4U6S17 Cs2Pd4U6S17 BaU2S5 SrU2S5 PbU2S5 Rb0.85U1.74S6 K0.91U1.79S6

+3 +3 +3b +4 +4 +4 +4 +4 +4 +4 +4 +4

2.768(1)−3.131(1) 2.822(1)−3.166(1) 2.872(1)−3.034(1) 2.755(1)−2.977(1) 2.734(1)−2.820(1) 2.762(1)−2.887(1) 2.753(1)−2.924(1) 2.730(1)−2.989(1) 2.749(1)−2.978(1) 2.765(1)−2.963(1) 2.775(3)−2.847(2) 2.761(2)−2.846(2)

this work 2 35 5 36 37 37 38 39 39 40 41

a

To facilitate comparisons in this table distances from the original cif files, where necessary, were rounded to three significant figures. bU3S5 also contains a seven-coordinate U4+ cation.

to 2.597(1) Å) agree with those observed in ScU8S17 (2.434(1) Å to 2.520(1) Å)3 and ScU3S6 (2.439(6) Å and 2.598(4) Å).2 These three compounds have octahedrally coordinated Sc3+. Resistivity Study. ScUS3 is a narrow band-gap semiconductor. Its resistivity decreases with increasing temperature from 130 Ω·cm at 300 K to 32 Ω·cm at 500 K, as shown in Figure 4. The corresponding Arrhenius plot is linear indicating a simple thermal excitation mechanism of the carriers with an activation energy of 0.09(1) eV.

Figure 3. Sc network in ScUS3 viewed down the [010] direction.

Important interatomic distances in ScUS3 are given in Table 2. All the distances are in good agreement with those reported earlier,1 but are more precise. The shortest S···S distance is 3.420(1) Å, and hence there are no S−S bonds. Thus, the formula may be written as Sc3+U3+(S2−)3.The U−S interatomic distances (2.768(1) Å to 3.131(1) Å) can be compared with

Figure 4. Variation of resistivity with temperature and the corresponding Arrhenius plot for a single crystal of ScUS3.

Magnetic Studies. The temperature dependence between 2 and 300 K of the magnetic susceptibility χ (= m/H) of ScUS3 at 1 kOe and 10 kOe is shown in Figure 5. The overall temperature dependence is complex, and clear differences were observed between ZFC and FC conditions at low temperatures. The χ value increases when the material is cooled from 300 to 200 K in accordance with the Curie−Weiss law. This is more obvious in Figure 6 where the inverse susceptibility (1/χ) versus T is shown. A fit of these data to the Curie−Weiss law 1/χ = (T − θW)/C affords a value of θW of 60(2) K and that of μeff = (7.997C)1/2 of 2.67(3) μB. As the temperature is lowered, χ decreases below ∼198 K (denoted as TN) followed by an abrupt increase at ∼75 K (denoted as Tc) (Figure 5). When the material is further cooled, the ZFC and FC curves start to deviate from one another below a certain field-dependent

Table 2. Selected Interatomic Lengths (Å) for ScUS3a U1−S1 U1−S1 U1−S2 U1···U1 Sc1−S1 Sc1−S2 Sc1···U1 Sc1···Sc1 S···S a

2.888(1) 3.131(2) 2.768(2) 3.750(1) 2.597(1) 2.492(1) 3.815(1) 3.750(1) 3.420(1)

×4 ×2 ×2 ×4 ×2

U has symmetry m2m; Sc has symmetry 2/m. C

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f.u.) than expected for typical ferromagnetism. Because the ferromagnetic ordering temperature (Tc ≈ 75 K) is well below the antiferromagnetic ordering temperature (TN ≈ 198 K), the ferromagnetic behavior at low temperatures is likely due to weak ferromagnetism from canted antiferromagnetic spins. This is consistent with the ferromagnetic behavior observed from the magnetic susceptibility and also with the magnetization data, namely, slow increase at low fields and a small moment even after rapid increase. The weak ferromagnetism often comes from antiferromagnets with finite antisymmetric exchange interaction via the so-called Dzyaloshinskii−Moriya (DM) interaction.27,28 The DM interaction involves superexchange interactions of a third ion with the magnetic ions not on a same plane with broken inversion symmetry, which is the case for ScUS3 (U−S−U superexchange path). Alternatively, it is also possible that a single-ion anisotropy (rather than double-ion anisotropy such as the DM interaction) is responsible for the weak ferromagnetism.29,30 More generally, according to the space group analysis, the DM interaction is allowed in orthorhombic ScUS3, in which the antiferromagnetic easy axis should be perpendicular to the weak ferromagnetic easy axis.31,32 Magnetic measurements on single crystals could give more insight into the existence of the weak ferromagnetism itself and its anisotropy. Unfortunately, no single crystals sufficiently large for such studies were obtained in the synthesis. Similar weak ferromagnetic behavior was observed in several UMQ3 compounds including CoUS3,7 CoUSe3,33 CrUSe3,33 VUSe3,33 and CrUS3.34 The detailed magnetic ground states of these compounds are more complicated owing to the magnetic moments of the transition metals. Indeed, CoUS3 has a noncollinear configuration of Co3+ moments, whereas CrUS3 shows c-type collinear antiferromagnetism for Cr3+. Nevertheless, the common feature of weak ferromagnetism that is observed in these compounds implies the importance of the antisymmetric exchange interaction of U3+ moments. Our observation of the weak ferromagnetism in ScUS3 more clearly demonstrates the importance of this interaction because Sc3+ is nonmagnetic. Now consider the paramagnetic phase of ScUS3 at high temperatures. The value of μeff of 2.67 μB is smaller than that of 3.62 μB for the U3+ free ion with L−S coupling. Furthermore, the Weiss temperature is +60 K, implying ferromagnetic coupling, which is seemingly inconsistent with the antiferromagnetic ordering with very high TN. We speculate that the discrepancies are related to the crystal field effect and to the fact that the measured temperature range is close to TN. Density Functional Theory Calculations. ScUS3 is calculated to be ferromagnetic in agreement with experiments, and from its total density of states (see the top plot of Figure 8), it has a small density of states at the Fermi level. Because smearing effects limit the resolution it is not possible to tell whether ScUS3 is a poor metal or a semiconductor with a small gap. The computed partial density of states of the inequivalent atoms in the cell (Figure 8) show that the states around the Fermi level correspond to U-f and Sc-d states. The up and down spin channels for U are different, and this induces a small magnetic polarization on the other atoms, which is best seen on the Sc-d states around and above the Fermi level.

Figure 5. Temperature dependence of molar magnetic susceptibility χ of ScUS3 at different magnetic fields. (inset) Expansion of the hightemperature region. Solid symbols represent FC data, and hollow symbols indicate ZFC data.

Figure 6. Inverse magnetic susceptibility as a function of temperature. The line is the linear fit between 220 and 300 K.

temperature (denoted as Tirr), and χ for the ZFC measurement eventually decreases again at lower temperatures. The observed temperature dependence of χ suggests that there are at least two magnetic transitions present: (i) paramagnetic to antiferromagnetic ordering at TN and (ii) antiferromagnetic to ferromagnetic ordering at Tc. The existence of Tirr and the complex temperature dependence below Tirr also suggest the existence of ferromagnetism, in which the bulk magnetic moment is highly dependent on magnetic domains and cooling conditions. The magnetization data at different temperatures taken after ZFC from 298 K are shown in Figure 7. At first glance, the

Figure 7. Magnetization data taken at temperatures of 5, 10, 20, and 130 K. The sample was zero-field cooled from 298 K.

magnetization behavior looks like that of a typical ferromagnetic material: large hysteresis and slow increase of magnetization at high fields. At low fields, however, the magnetization increases rather slowly, almost linearly with field until it increases rapidly above certain fields (3, 9, and 18 kOe for 20, 10, and 5 K, respectively). Furthermore, the magnetization value after the rapid increase is somewhat smaller (∼0.07 μB/

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CONCLUSIONS Black needle-shaped single crystals of ScUS3 were obtained in high yield by reaction of stoichiometric amounts of Sc, U, and S at 1173 K. ScUS3 crystallizes in the FeUS3 structure type with D

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four formula units in the space group D17 2h−Cmcm of the orthorhombic system. In the structure the Sc atoms are connected to six S atoms in a slightly distorted octahedral fashion forming two-dimensional infinite layers perpendicular to the b-axis. These layers are separated by U atoms that are coordinated to eight S atoms in a bicapped trigonal-prismatic arrangement. The crystal structure does not possess any S−S single bonds, and hence charge balance can be achieved as Sc3+U3+(S2−)3. That the U−S interatomic distances in ScUS3 are longer than those in related U4+ sulfides also corroborates the presence U3+ in ScUS3. The high temperature-dependent resistivity of a single crystal of ScUS3 shows semiconducting behavior with an activation energy of 0.09(1) eV. A magnetic study on ground single crystals of ScUS3 shows complex temperature dependence with two magnetic transitions: paramagnetic to antiferromagnetic at TN = 198 K and antiferromagnetic to ferromagnetic at TC = 75 K. At high temperatures the magnetic susceptibility obeys the Curie− Weiss law with the Weiss temperature being 60 K and the effective magnetic moment being 2.67(3) μB. The ferromagnetic behavior at low temperatures is likely due to weak ferromagnetism from canted antiferromagnetic spins. DFT calculations suggest that ScUS3 is ferromagnetic and either a poor metal or a semiconductor with a small gap.

ASSOCIATED CONTENT

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AUTHOR INFORMATION

REFERENCES

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Figure 8. Total (upper plot) and partial density of states (lower plots) of ScUS3.

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Article

S Supporting Information *

Crystallographic file in CIF format for ScUS3. This material is available free of charge via the Internet at http://pubs.acs.org. Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Use was made of the IMSERC X-ray facility at Northwestern University, supported by the International Institute of Nanotechnology. A portion of this work was performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative Agreement No. DMR−1157490 by the State of Florida and by the Department of Energy. C.D.M. was supported by the U. S. Department of Energy, Office of Basic Energy Sciences, under contract DEAC02-06CH11357. E

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Inorganic Chemistry (39) Prakash, J.; Tarasenko, M. S.; Mesbah, A.; Lebègue, S.; Malliakas, C. D.; Ibers, J. A. Inorg. Chem. 2014, 53, 11626−11632. (40) Bugaris, D. E.; Wells, D. M.; Yao, J.; Skanthakumar, S.; Haire, R. G.; Soderholm, L.; Ibers, J. A. Inorg. Chem. 2010, 49, 8381−8388. (41) Mizoguchi, H.; Gray, D.; Huang, F. Q.; Ibers, J. A. Inorg. Chem. 2006, 45, 3307−3311.

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