Single crystal growth from light, volatile, and reactive materials using lithium and calcium flux

We present a method for the solution growth of single crystals from reactive Li and Ca melts and its application to the synthesis of several, representative compounds. Among these, single crystalline Li3N, Li2(Li{1-x}Tx)N with T = {Mn, Fe, Co}, LiCaN, Li2C2, LiRh, and LiIr from Li-rich flux as well as Ca2N, CaNi2, CaNi3, YbNi2, Y2Ni7, and LaNi5 from Ca-rich flux could be obtained. Special emphasize is given on the growth of nitrides using commercially available Li3N and Ca3N2 powders as the nitrogen source instead of N2 gas.Comment: 40 pages, 20 figures, reference list update

Single crystal growth and characterization of the large-unit-cell compound Cu13Ba

Single crystals of Cu$_{13}$Ba were successfully grown out of Ba-Cu self flux. Temperature dependent magnetization, $M(T)$, electrical resistivity, $\rho(T)$, and specific heat, $C_p(T)$, data are reported. Isothermal magnetization measurements, $M(H)$, show clear de Haas-van Alphen oscillations at $T$ = 2 K for applied fields as low as $\mu_0H$ = 1T. An anomalous behavior of the magnetic susceptibility is observed up to $T$ ~ 50K reflecting the effect of de Haas-van Alphen oscillations at fairly high temperatures. The field- and temperature-dependencies of the magnetization indicate the presence of diluted magnetic impurities with a concentration of the order of 0.01at.%. Accordingly, the minimum and lower temperature rise observed in the electrical resistivity at and below $T$ = 15K is attributed to the Kondo impurity effect.Comment: 6 pages, 8 figures, accepted for publication in J. Alloys Comp

Structural trends from a consistent set of single-crystal data of REFeAsO (RE = La, Ce, Pr, Nd, Sm, Gd, and Tb)

A new crystal growth technique for single-crystals of REFeAsO (RE = La, Ce, Pr, Nd, Sm, Gd, and Tb) using NaI/KI as flux is presented. Crystals with a size up to 300 $\mu$m were isolated for single-crystal X-ray diffraction measurements. Lattice parameters were determined by LeBail fits of X-ray powder data against LaB6 standard. A consistent set of structural data is obtained and interpreted in a hard-sphere model. Effective radii for the rare-earth metal atoms for REFeAsO are deduced. The relation of the intra- and inter-plane distances of the arsenic atoms is identified as limiter of the phase formation, and its influence on Tc is discussed.Comment: 8 pages, 11 figures, 3 tables, fig. 6 changed to numerical plot, minor changes to the text, accepted for publication in PR

Structural and magnetic transition in CeFeAsO: separated or connected?

Using an adapted Sn-flux growth technique we obtained comparatively large CeFeAsO single crystals of better quality than previously reported polycrystals or single crystals, as evidenced by much sharper anomalies at the structural and magnetic phase transitions as well as a much higher residual resistivity ratio of 12. In the magnetically ordered phase we observe a very pronounced metallic behavior of the in-plane resistivity, which excludes a Mott insulator regime at low temperature. The separation Delta_T = T_0 - T_N between structural and magnetic ordering temperatures decreases with increasing sample quality, from 18 K in the initial reports to 6 K in the present single crystals, demonstrating that this separation is not an intrinsic property of the RFeAsO systems. Our results indicate that the coupling between magnetic ordering and structural distortion is very similar in AFe2As2 and RFeAsO type of compounds, much more similar than previously thought. The implications of our experimental results give arguments both in favor and against the nematic phase model.Comment: published in PRB with the title 'Coupling between the structural and magnetic transition in CeFeAsO

Ferromagnetic ordering of linearly coordinated Co ions in LiSr2_2[CoN2_2]

LiSr$_2$[CoN$_2$] single crystals were successfully grown out of Li-rich flux. Temperature- and field-dependent measurements of the magnetization in the range of $T = 2 - 300$ K and up to $\mu_{0}\textit{H} = 7$ T as well as measurements of the heat capacity are presented. Ferromagnetic ordering emerges below $T_C = 44$ K and comparatively large coercivity fields of $\mu_0H = 0.3$ T as well as pronounced anisotropy are observed upon cooling. Polycrystalline samples of the Ca analog LiCa$_2$[CoN$_2$] were obtained and investigated in a similar way. In both compounds Co manifests orbital contributions to the magnetic moment and large single-ion anisotropy that is caused by second-order Spin-orbit coupling. Quantum chemistry calculations reveal a magnetic anisotropy energy of 7 meV, twice as large as the values reported for similar Co $d^{8}$ systems.Comment: 21 pages, 6 figures, 5 table

Cooperative quantum tunneling of the magnetization in Fe-doped Li3_3N

The spin-reversal in dilute Li$_2$(Li$_{1-x}$Fe$_{x}$)N with $x < 1$ % is dominated by resonant quantum tunneling of spatially well-separated states. We report on the effect of finite couplings between those states that give rise to cooperative, simultaneous quantum tunneling of two spins. This phenomenon, known as spin-spin cross relaxation, effectively elucidates the fine-structure observed in isothermal magnetization loops, a previously unresolved aspect. Temperature and field-dependent magnetization measurements were conducted over a range from T = 2 K to 300 K in applied fields of up to $\mu_0H$ = 7 T. Magnetic dipole fields are computed numerically. Our findings affirm the absence of stoichiometric defects in Li$_2$(Li$_{1-x}$Fe$_{x}$)N and underscore its exemplary suitability as a model system for investigating spin-reversal processes at the microscopic level. This is attributed to its comparatively simple crystal structure, the availability of large single crystals, elevated characteristic energies, and well-defined energy levelsComment: 7 pages, 4 figure

Anisotropic electrical resistivity of LaFeAsO: evidence for electronic nematicity

Single crystals of LaFeAsO were successfully grown out of KI flux. Temperature dependent electrical resistivity was measured with current flow along the basal plane, \rho_perpend(T), as well as with current flow along the crystallographic c-axis, \rho_parallel(T), the latter one utilizing electron beam lithography and argon ion beam milling. The anisotropy ratio was found to lie between \rho_parallel/\rho_perpend = 20 - 200. The measurement of \rho_perpend(T) was performed with current flow along the tetragonal [1 0 0] direction and along the [1 1 0] direction and revealed a clear in-plane anisotropy already at T \leq 175 K. This is significantly above the orthorhombic distortion at T_0 = 147 K and indicates the formation of an electron nematic phase. Magnetic susceptibility and electrical resistivity give evidence for a change of the magnetic structure of the iron atoms from antiferromagnetic to ferromagnetic arrangement along the c-axis at T^\ast = 11 K.Comment: 10 pages, 6 figures, minor change

Avoided ferromagnetic quantum critical point in CeRuPO

CeRuPO is a rare example of a ferromagnetic (FM) Kondo-lattice system. External pressure suppresses the ordering temperature to zero at about $p_c\approx3$ GPa. Our ac-susceptibility and electrical-resistivity investigations evidence that the type of magnetic ordering changes from FM to antiferromagnetic (AFM) at about $p^*\approx0.87$ GPa. Studies in applied magnetic fields suggest that ferromagnetic and antiferromagnetic correlations compete for the ground state at $p>p^*$, but finally the AFM correlations win. The change in the magnetic ground-state properties is closely related to the pressure evolution of the crystalline-electric-field level (CEF) scheme and the magnetic Ruderman-Kittel-Kasuya-Yosida (RKKY) exchange interaction. The N\'{e}el temperature disappears abruptly in a first-order-like fashion at $p_c$, hinting at the absence of a quantum critical point. This is consistent with the low-temperature transport properties exhibiting Landau-Fermi-liquid (LFL) behavior in the whole investigated pressure range up to 7.5 GPa.Comment: 12 figure

Iron single crystal growth from a lithium-rich melt

\alpha-Fe single crystals of rhombic dodecahedral habit were grown from a melt of Li$_{84}$N$_{12}$Fe$_{\sim 3}$. Crystals of several millimeter along a side form at temperatures around $T \approx 800^\circ$C. Upon further cooling the growth competes with the formation of Fe-doped Li$_3$N. The b.c.c. structure and good sample quality of \alpha-Fe single crystals were confirmed by X-ray and electron diffraction as well as magnetization measurements and chemical analysis. A nitrogen concentration of 90\,ppm was detected by means of carrier gas hot extraction. Scanning electron microscopy did not reveal any sign of iron nitride precipitates.Comment: 13 pages, 4 figure

Interplay between Co-3d and Ce-4f magnetism in CeCoAsO

We have investigated the ground state properties of polycrystalline CeCoAsO by means of magnetization, specific heat and solid state NMR. Susceptibility and specific-heat measurements suggest a ferromagnetic order at about, $T_\mathrm{C}$=75 K. No further transitions are found down to 2 K. At 6.5 K a complex Schottky type of anomaly shows up in the specific heat results. The interplay between Ce-4f and Co-3d magnetism being responsible for that anomaly is discussed. Furthermore $^{75}$As NMR investigations have been performed to probe the magnetism on a microscopic scale. As-NMR spectra are analysed in terms of first and second order quadrupolar interaction. The anisotropic shift component $K_{\mathrm{ab}}$ and $K_{\mathrm{c}}$ could be derived from the $^{75}$As powder spectra. Towards lower temperature a strong shift anisotropy was found. Nonetheless $K_{\mathrm{iso}}$ tracks the bulk susceptibility down to $T=$50 K very well. Furthermore the presence of weak correlations among the Ce ions in the ferromagnetic state is discussed. The observed increase of $C/T$ towards lower temperatures supports this interpretation.Comment: 6 pages, 4 figures, Accepted in Physical Review