Search

The Co2B system shows a significant magnetovolume effect around its Curie temperature which makes it potentially attractive for magnetocaloric applications or thermomagnetic power generation, as a large coupling between the lattice and spin degrees of freedom is expected. We report on the synthesis of a series of Co2-xMnxB alloys and the investigation of their properties. The structural analysis indicates a single phase behavior up to x = 0.8 with no structural symmetry changes throughout the series. Measurements of both, macroscopic and local magnetic properties, reveal an anomalous behavior of the spontaneous magnetization, Curie temperature, and element-specific magnetic moments as a function of manganese concentration. The elemental contributions to the magnetization are analyzed using nuclear magnetic resonance (NMR) studies. Density functional theory (DFT) calculations guide us in the understanding of the origin of the observed anomaly, which is due to a complex magnetic coupling behavior between Mn atoms, which significantly affects the corresponding exchange interactions. The magnetocaloric properties of the Co2-xMnxB alloys show that the maximum entropy change peak temperature can be shifted between room temperature and 450 K upon variation of the manganese concentration without significant impact on the magnetocaloric response. The highest entropy change of -1.37 Jkg(-1)K(-1) at 442 K is obtained for x = 0.1 for a field change of 2 T. This value is, however, quite low for any possible magnetocaloric or thermomagnetic power generation applications. Nevertheless, the good agreement between the advanced characterization and theory gives a deeper understanding of the Co2-xMnxB material system which can in the future be extended to other systems. (C) 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

We discuss the impact of concomitant substitution of Fe by Mn and La by Y in optimally F-doped ${\mathrm{LaFeAsO}}_{0.89}{\mathrm{F}}_{0.11}$. Mn has a known poisoning effect on superconductivity which is particularly strong in the La1111 system, where 0.2% of Mn were reported to completely suppress superconductivity. Through isovalent substitution of La by the much smaller Y we are able to inflict chemical pressure on the structure, which we show is stabilizing the superconducting state, resulting in a drastically larger amount of Mn needed to completely quench superconductivity. Interestingly, we find that the lattice parameter $\mathit{c}$ changes significantly even for small amounts of Mn substitution within a series, which is unexpected taking only the differences between ionic radii into account. We discuss our findings in the light of electron localization caused by small amounts of paramagnetic Mn impurities in ${\mathrm{La}}_{1\ensuremath{-}y}{\mathrm{Y}}_{y}{\mathrm{Fe}}_{1\ensuremath{-}x}{\mathrm{Mn}}_{x}{\mathrm{AsO}}_{0.89}{\mathrm{F}}_{0.11}$ also indicated by resistivity and M\"o\ss{}bauer measurements.

We investigated the structure-property relationship of Co$_2$MnSi Heusler thin films upon the irradiation with He$^+$ ions. The variation of the crystal structure with increasing ion fluence has been probed using nuclear magnetic resonance (NMR) and transmission electron microscopy (TEM), and associated with the corresponding changes of the magnetic behavior. A decrease of both the structural order and the moment in saturation is observed. Specifically, we detect a direct transition from a highly $L2_1$-ordered to a fully $A2$-disordered structure type and quantify the evolution of the $A2$ structural contribution as a function of ion fluence. Complementary TEM analysis reveals a spatially-resolved distribution of the $L2_1$ and $A2$ phases showing that the $A2$ disorder starts at the upper part of the films. The structural degradation in turn leads to a decreasing magnetic moment in saturation in response to the increasing fluence., Comment: 9 pages, 5 figures

The increasing interest in nanoscale materials goes hand in hand with the challenge to reliably characterize the chemical compositions and structural features of nanosized objects in order to relate those to their physical properties. Despite efforts, the analysis of the chemical composition of individual multi-element nanoparticles remains challenging—from the technical point of view as well as from the point of view of measurement statistics. Here, we demonstrate that zero-field solid-state nuclear magnetic resonance (NMR) complements local, single particle transmission electron microscopy (TEM) studies with information on a large assembly of chemically complex nanoparticles. The combination of both experimental techniques gives information on the local composition and structure and provides an excellent measurement statistic through the corresponding NMR ensemble measurement. This analytical approach is applicable to many kinds of magnetic materials and therefore may prove very versatile in the future research of particulate magnetic nanomaterials.

The S=1/2 Heisenberg spin chain compound SrCuO2 doped with different amounts of nickel (Ni), palladium (Pd), zinc (Zn) and cobalt (Co) has been studied by means of Cu nuclear magnetic resonance (NMR). Replacing only a few of the S=1/2 Cu ions with Ni, Pd, Zn or Co has a major impact on the magnetic properties of the spin chain system. In the case of Ni, Pd and Zn an unusual line broadening in the low temperature NMR spectra reveals the existence of an impurity-induced local alternating magnetization (LAM), while exponentially decaying spin-lattice relaxation rates $T_1^{-1}$ towards low temperatures indicate the opening of spin gaps. A distribution of gap magnitudes is proven by a stretched spin-lattice relaxation and a variation of $T_1^{-1}$ within the broad resonance lines. These observations depend strongly on the impurity concentration and therefore can be understood using the model of finite segments of the spin 1/2 antiferromagnetic Heisenberg chain, i.e. pure chain segmentation due to S = 0 impurities. This is surprising for Ni as it was previously assumed to be a magnetic impurity with S = 1 which is screened by the neighboring copper spins. In order to confirm the S = 0 state of the Ni, we performed x-ray absorption spectroscopy (XAS) and compared the measurements to simulated XAS spectra based on multiplet ligand-field theory. Furthermore, Zn doping leads to much smaller effects on both the NMR spectra and the spin-lattice relaxation rates, indicating that Zn avoids occupying Cu sites. For magnetic Co impurities, $T_1^{-1}$ does not obey the gap like decrease, and the low-temperature spectra get very broad. This could be related to the increase of the Neel temperature which was observed by recent muSR and susceptibility measurements, and is most likely an effect of the impurity spin $S\neq0$., 14 pages, 10 figures

The cubic double perovskite Ba$_2$YIrO$_6$ has been investigated by the local probe techniques nuclear magnetic resonance ($^{89}$Y NMR) and muon spin rotation (muSR). Both methods confirm the absence of magnetic long-range order in this compound but find evidence for diluted localized paramagnetic moments. NMR spin-lattice relaxation rate 1/T1 measurements suggest a slowing down of localized spin moments at low temperatures. An increase of the muSR spin-lattice relaxation rate lambda confirms the presence of weak magnetism in Ba$_2$YIrO$_6$ . However, these findings cannot be explained by the recently suggested excitonic type of magnetism. Instead, they point towards tiny amounts of localized paramagnetic spin centers leading to this magnetic response on the background of a simple nonmagnetic ground state of the 5d$^4$ ($J=0)$ electronic configuration of Ir$^{5+}$., Comment: 8 pages, 7 figures

Using nuclear quadrupole resonance, the phase diagram of $1111 R{\mathrm{FeAsO}}_{1\ensuremath{-}x}{\mathrm{F}}_{x}$ ($R=\text{La}$, Ce, Sm) iron pnictides is constructed as a function of the local charge distribution in the paramagnetic state, which features low-doping-like (LD-like) and high-doping-like (HD-like) regions. Compounds based on magnetic rare earths (Ce, Sm) display a unified behavior, and comparison with La-based compounds reveals the detrimental role of static iron $3d$ magnetism on superconductivity, as well as a qualitatively different evolution of the latter at high doping. It is found that the LD-like regions fully account for the orthorhombicity of the system, and are thus the origin of any static iron magnetism. Orthorhombicity and static magnetism are not hindered by superconductivity but limited by dilution effects, in agreement with two-dimensional (2D) (respectively three-dimensional) nearest-neighbor square lattice site percolation when the rare earth is nonmagnetic (respectively magnetic). The LD-like regions are not intrinsically supportive of superconductivity, contrary to the HD-like regions, as evidenced by the well-defined Uemura relation between the superconducting transition temperature and the superfluid density when accounting for the proximity effect. This leads us to propose a complete description of the interplay of ground states in 1111 pnictides, where nanoscopic regions compete to establish the ground state through suppression of superconductivity by static magnetism, and extension of superconductivity by proximity effect.

The $S=1/2$ antiferromagnetic Heisenberg spin chain compound ${\mathrm{Sr}}_{2}{\mathrm{CuO}}_{3}$ doped with $1%$ and $2%$ of Ni impurities has been studied by means of $^{63}\mathrm{Cu}$ nuclear magnetic resonance. A strong decrease of the spin-lattice relaxation rate ${T}_{1}^{\ensuremath{-}1}$ at low temperatures points toward a spin gap, while a stretching exponent $\ensuremath{\lambda}l1$ and a frequency dependence of ${T}_{1}^{\ensuremath{-}1}$ indicate that this spin gap varies spatially and should rather be characterized as a spin pseudogap. The magnitude of the spin pseudogap scales with doping level. Our results therefore evidence the finite-size character of this phenomenon. Moreover, an unusual narrowing of the low-temperature NMR lines reveals the suppression of the impurity-induced staggered paramagnetic response with increasing doping level.

$^{19}\mathrm{F}$ NMR measurements in optimally electron-doped ${\mathrm{La}}_{1\text{\ensuremath{-}}y}{\mathrm{Y}}_{y}{\mathrm{Fe}}_{1\text{\ensuremath{-}}x}{\mathrm{Mn}}_{x}{\mathrm{AsO}}_{0.89}{\mathrm{F}}_{0.11}$ superconductors are presented. The effect of Mn doping on the superconducting phase is studied for two series of compounds $(y=0$ and $y=0.2)$ where the chemical pressure is varied by substituting La with Y. In the $y=0.2$ series superconductivity is suppressed for Mn contents an order of magnitude larger than for $y=0$. For both series a peak in the $^{19}\mathrm{F}$ NMR nuclear spin-lattice relaxation rate $1/{T}_{1}$ emerges upon Mn doping and becomes significantly enhanced on approaching the quantum phase transition between the superconducting and magnetic phases. $^{19}\mathrm{F}$ NMR linewidth measurements show that for similar Mn contents magnetic correlations are more pronounced in the $y=0$ series, at variance with what one would expect for $\stackrel{P\vec}{Q}=(\ensuremath{\pi}/a,0)$ spin correlations. These observations suggest that Mn doping tends to reduce fluctuations at $\stackrel{P\vec}{Q}=(\ensuremath{\pi}/a,0)$ and to enhance other low-frequency modes. The effect of this transfer of spectral weight on the superconducting pairing is discussed along with the charge localization induced by Mn.

We report $^{63}$Cu nuclear magnetic resonance and muon spin rotation measurements on the S=1/2 antiferromagnetic Heisenberg spin chain compound Sr$_{1.9}$Ca$_{0.1}$CuO$_3$. An exponentially decreasing spin-lattice relaxation rate 1/T$_1$ indicates the opening of a spin gap. This behavior is very similar to what has been observed for the cognate zigzag spin chain compound Sr$_{0.9}$Ca$_{0.1}$CuO$_2$, and confirms that the occurrence of a spin gap upon Ca doping is independent of the interchain exchange coupling $J'$. Our results therefore generally prove the appearance of a spin gap in an antiferromagnetic Heisenberg spin chain induced by a local bond disorder of the intrachain exchange coupling $J$. A low temperature upturn of 1/T$_1$ evidences growing magnetic correlations. However, zero field muon spin rotation measurements down to 1.5 K confirm the absence of magnetic order in this compound which is most likely suppressed by the opening of the spin gap.

A superconducting-to-magnetic transition is reported for LaFeAsO0.89F0.11 where a per-thousand amount of Mn impurities is dispersed. By employing local spectroscopic techniques like muon spin rotation (muSR) and nuclear quadrupole resonance (NQR) on compounds with Mn contents ranging from x = 0.025% to x = 0.75 %, we find that the electronic properties are extremely sensitive to the Mn impurities. In fact, a small amount of Mn as low as 0.2% suppresses superconductivity completely. Static magnetism, involving the FeAs planes, is observed to arise for x > 0.1% and becomes further enhanced upon increasing Mn substitution. Also a progressive increase of low-energy spin fluctuations, leading to an enhancement of the NQR spin-lattice relaxation rate 1/T1, is observed upon Mn substitution. The analysis of 1/T1 for the sample closest to the crossover between superconductivity and magnetism (x = 0.2%) points toward the presence of an antiferromagnetic quantum critical point around that doping level.

We report $^{7}$Li, $^{29}$Si, and $^{13}$C NMR studies of two different carbon-rich SiCN ceramics SiCN-1 and SiCN-3 derived from the preceramic polymers polyphenylvinylsilylcarbodiimide and polyphenylvinylsilazane, respectively. From the spectral analysis of the three nuclei at room temperature, we find that only the $^{13}$C spectrum is strongly influenced by Li insertion/extraction, suggesting that carbon phases are the major electrochemically active sites for Li storage. Temperature and Larmor frequency ($\omega_L$) dependences of the $^7$Li linewidth and spin-lattice relaxation rates $T_1^{-1}$ are described by an activated law with the activation energy $E_A$ of 0.31 eV and the correlation time $\tau_0$ in the high temperature limit of 1.3 ps. The $3/2$ power law dependence of $T_1^{-1}$ on $\omega_L$ which deviates from the standard Bloembergen, Purcell, and Pound (BPP) model implies that the Li motion on the $\mu$s timescale is governed by continuum diffusion mechanism rather than jump diffusion. On the other hand, the rotating frame relaxation rate $T_{1\rho}^{-1}$ results suggest that the slow motion of Li on the ms timescale may be affected by complex diffusion and/or non-diffusion processes., Comment: 28 pages with double line spacing, 7 figures and 2 tables, accepted version in Journal of Power Sources

We report resistivity and upper critical field B c 2 ( T ) data for disordered (As-deficient) LaO 0.9 F 0.1 FeAs 1 - δ in a wide temperature and high field range up to 60 T. These samples exhibit a slightly enhanced superconducting transition at T c = 28.5 K and a significantly enlarged slope d B c 2 / d T = - 5.4 T / K near T c which contrasts with a flattening of B c 2 ( T ) starting near 23 K above 30 T. The latter evidences Pauli-limiting behaviour (PLB) with B c 2 ( 0 ) ≈ 63 T . We compare our results with B c 2 ( T ) -data from the literature for clean and disordered samples. Whereas clean samples show almost no PLB for fields below 60–70 T, the hitherto unexplained pronounced flattening of B c 2 ( T ) for applied fields H ‖ ab observed for several disordered closely related systems is interpreted also as a manifestation of PLB. Consequences are discussed in terms of disorder effects within the frames of (un)conventional superconductivity, respectively.

The evolution of low-energy spin dynamics in the iron-based superconductor LaFeAsO$_{1-x}$F$_x$ was studied over a broad doping, temperature, and magnetic field range (x = 0 - 0.15, T up to 480K, H up to 30T) by means of As nuclear magnetic resonance (NMR). An enhanced spin-lattice relaxation rate divided by temperature, 1/T1T, in underdoped superconducting samples (x = 0.045, 0.05 and 0.075) suggests the presence of antiferromagnetic spin fluctuations, which are strongly reduced in optimally-doped (x = 0.10) and completely absent in overdoped (x = 0.15) samples. In contrast to previous analysis, Curie-Weiss fits are shown to be insufficient to describe the data over the whole temperature range. Instead, a BPP-type model is used to describe the occurrence of a peak in 1/T1T clearly above the superconducting transition, reflecting a progressive slowing down of the spin fluctuations down to the superconducting phase transition., Comment: 10 pages, 10 figures

authoren Orbital ordering has recently emerged as another important state in iron-based superconductors, and its role for superconductivity as well as its connection to magnetic order and orthorhombic lattice distortion are heavily debated. In order to search for signatures of this so-called nematic phase in oxypnictides, we revisit the normal state properties of the pnictide superconductor LaFeAsO1−x Fx with a focus on resistivity, Nernst effect, thermal expansion, and As nuclear magnetic resonance (NMR) data. The transport properties at the underdoped level exhibit pronounced anomalies at about the same temperature where undoped LaFeAsO develops long-range nematic ordering, i.e., at about 160 K. Furthermore, the As-NMR spin-lattice relaxation rate reveals a progressive slowing down of spin fluctuations. Yet, long-range magnetic order and also a detectable orthorhombic lattice distortion are absent. Thus, we conclude from the data that short-range orbital-nematic ordering or a slowly fluctuating form of it sets in near 160 K. Remarkably, all anomalies in the transport and also the indications of slow spin fluctuations disappear close to optimal doping which suggests that in LaFeAsO1−x Fx the nematic phase actually competes with superconductivity. Schematic electronic phase diagram of LaFeAsO1−x Fx.

We report magnetization measurements of As-deficient LaO_0.9F_0.1FeAs_1-delta (delta about 0.06) samples with improved superconducting properties as compared with As-stoichiometric optimally doped La-1111 samples. In this As-deficient system with almost homogeneously distributed As-vacancies (AV), as suggested by the (75)As-nuclear quadrupole resonance (NQR) measurements,we observe a strong enhancement of the spin-susceptibility by a factor of 3-7. This observation is attributed to the presence of an electronically localized state around each AV, carrying a magnetic moment of about 3.2 mu_Bohr per AV or 0.8 mu_Bohr/Fe atom. From theoretical considerations we find that the formation of a local moment on neighboring iron sites of an AV sets in when the local Coulomb interaction exceeds a critical value of about 1.0 eV in the dilute limit. Its estimated value amounts to ~ 2.5 eV and implies an upper bound of ~ 2 eV for the Coulomb repulsion at Fe sites beyond the first neighbor-shell of an AV. Electronic correlations are thus moderate/weak in doped La-1111. The strongly enhanced spin susceptibility is responsible for the Pauli limiting behavior of the superconductivity that we observe in As-deficient LaO_0.9F_0.1FeAs_1-delta. In contrast, no Pauli limiting behavior is found for the optimally doped, As-stoichiometric LaO_0.9F_0.1FeAs superconductor in accord with its low spin susceptibility.

We report a comparative study of (63)Cu nuclear magnetic resonance spin lattice relaxation rates T(1)(-1) on undoped SrCuO(2) and Ca-doped Sr(0.9)Ca(0.1)CuO(2) spin chain compounds. A temperature independent T(1)(-1) is observed for SrCuO(2) as expected for an S=1/2 Heisenberg chain. Surprisingly, we observe an exponential decrease of T(1)(-1) for T

We report a comparative study of (63)Cu nuclear magnetic resonance spin lattice relaxation rates T(1)(-1) on undoped SrCuO(2) and Ca-doped Sr(0.9)Ca(0.1)CuO(2) spin chain compounds. A temperature independent T(1)(-1) is observed for SrCuO(2) as expected for an S=1/2 Heisenberg chain. Surprisingly, we observe an exponential decrease of T(1)(-1) for T90 K in the Ca-doped sample evidencing the opening of a spin gap. The data analysis within the J(1)-J(2) Heisenberg model employing density-matrix renormalization group calculations suggests an impurity driven small alternation of the J(2)-exchange coupling as a possible cause of the spin gap.

We report $^{75}\text{A}\text{s}$ nuclear magnetic resonance measurements of the spin-lattice relaxation in the superconducting (SC) state of ${\text{LaFeAsO}}_{0.9}{\text{F}}_{0.1}$ and As-deficient ${\text{LaFeAs}}_{1\ensuremath{-}\ensuremath{\delta}}{\text{O}}_{0.9}{\text{F}}_{0.1}$. The temperature behavior of $1/{T}_{1}$ below ${T}_{c}$ changes drastically from a ${T}^{3}$ dependence for ${\text{LaFeAsO}}_{0.9}{\text{F}}_{0.1}$ to a ${T}^{5}$ dependence for the As-deficient sample. These results, together with the previously reported unexpected increase in ${T}_{c}$ and the slope of the upper critical field near ${T}_{c}$ for the As-deficient sample, are discussed in terms of nonuniversal SC gaps in Fe pnictides and the effect of As deficiency as an exotic case where nonmagnetic ``smart'' impurities even stabilize an ${s}_{\ifmmode\pm\else\textpm\fi{}}$-wave superconductor or within a scenario of a disorder-driven change to ${s}_{++}$ superconductivity.

We have studied the interplay of magnetism and superconductivity in ${\text{LaFeAsO}}_{1\ensuremath{-}x}{\text{F}}_{x}$ and $\text{Ca}{({\text{Fe}}_{1\ensuremath{-}x}{\text{Co}}_{x})}_{2}{\text{As}}_{2}$. While antiferromagnetic spin-density wave formation is suppressed and superconductivity evolves, all samples show a doping-independent strong increase in the normal-state susceptibility upon heating which appears a general feature of iron pnictides. The data provide evidence for robust local antiferromagnetic correlations persisting even in the superconducting regime of the phase diagram.

A powerful tool to probe the electronic charge distribution in correlated oxides is nuclear magnetic/quadrupole resonance (NMR/NQR). Indeed, through sensitivity to the electric field gradient (EFG), NMR/NQR allows to probe locally the symmetry of the charge distribution, its homogeneity, as well as its sensitivity to structural and doping changes. In context of our own results, we discuss here the state of knowledge in iron pnictides. It appears that the iron pnictides feature a complex behaviour of their charge distribution, with a non-trivial link between the measured EFG and the structural and doping variations.

The charge distribution in RFeAsO$_{1-x}$F$_x$ (R=La, Sm) iron pnictides is probed using As nuclear quadrupole resonance. Whereas undoped and optimally-doped or overdoped compounds feature a single charge environment, two charge environments are detected in the underdoped region. Spin-lattice relaxation measurements show their coexistence at the nanoscale. Together with the quantitative variations of the spectra with doping, they point to a local electronic order in the iron layers, where low- and high-doping-like regions would coexist. Implications for the interplay of static magnetism and superconductivity are discussed., Comment: 4 pages

We report $^{63,65}\mathrm{Cu}$ nuclear quadrupole resonance (NQR) measurements on slightly underdoped $\mathrm{Nd}{\mathrm{Ba}}_{2}{\mathrm{Cu}}_{3}{\mathrm{O}}_{6+y}$ heavily doped by Ni and Zn impurities. Owing to the impurity doping, superconductivity is fully suppressed in both cases. The Ni strongly enhances magnetic correlations and induces a wipeout of the NQR signal comparable to that found in stripe ordered lanthanum cuprates. In contrast, the magnetism is suppressed in the Zn doped sample where no wipeout effect is observed and the nuclear spin relaxation rate is reduced. Our findings are in a striking correspondence with the different impact of Ni and Zn impurities on the charge pseudogap evidenced by recent optical data, uncovering thereby a close relationship between the magnetic correlations and pseudogap phenomena.

We have performed 139 La, 57 Fe and 75 As nuclear magnetic resonance (NMR) measurements on aligned powders of the optimally doped LaO 0.9 F 0.1 FeAs superconductor. For all three nuclei, it is found that the spin lattice relaxation rates scale with one another, with magnitudes reflecting that the FeAs layers support the electronic properties. This scaling suggests a lack of any q -space structure in the dynamical spin susceptibility, contrary to what may be expected in the presence of antiferromagnetic correlations. Rather, our results are more compatible with simple quasi-particle scattering. Furthermore, the 75 As relaxation rate decreases linearly from 480 K down to the superconducting transition temperature, making pseudogap fits inadequate. The decrease of the dynamic spin susceptibility with decreasing temperature is compatible with a decrease of the density of states, rather than a change of correlations in q -space.

We have investigated slightly underdoped NdBa 2 (Cu,Zn,Ni) 3 O 7− δ with magnetic Ni and non-magnetic Zn impurities by 63 Cu nuclear quadrupole resonance (NQR). The larger ionic radius of the Nd compared to Y made it possible to incorporate higher amounts of Zn and Ni impurities (up to 12% in our samples), and thereby superconductivity is completely suppressed. The 63 Cu NQR spectra are comparable to similar doped YBCO samples, but are shifted about ≈1.5 MHz to higher frequencies. By doping the samples with Ni the spectra are moderately broadened, whereas the broadening is stronger for Zn doping. The spin lattice relaxation rate, T 1 - 1 , is drastically enhanced by the large Nd moment, and thereby the pseudo gap is not visible in all of these samples.