Single crystals of the three-dimensional frustrated magnet and spin liquid candidate compound PbCuTe$_2$O$_6$ were grown using both the Travelling Solvent Floating Zone (TSFZ) and the Top-Seeded Solution Growth (TSSG) techniques. The growth conditions were optimized by investigating the thermal properties. The quality of the crystals was checked by polarized optical microscopy, X-ray Laue and X-ray powder diffraction, and compared to the polycrystalline samples. Excellent quality crystals were obtained by the TSSG method. Magnetic measurements of these crystals revealed a small anisotropy for different crystallographic directions in comparison with the previously reported data. The heat capacity of both single crystal and powder samples reveal a transition anomaly around 1 K. Curiously the position and magnitude of the transition are strongly dependent on the crystallite size and it is almost entirely absent for the smallest crystallites. A structural transition is suggested which accompanies the reported ferroelectric transition, and a scenario whereby it becomes energetically unfavourable in small crystallites is proposed.
Understanding the electronic behavior of Ni$^{2+}$ in a square planar environment of oxygen is the key to unravel the origin of the recently discovered superconductivity in the hole doped nickelate Nd$_{0.8}$Sr$_{0.2}$NiO$_2$. To identify the major similarities/dissimilarities between nickelate and cuprate superconductivity, the study of the electronic structure of Ni$^{2+}$ and Cu$^{2+}$ in an identical square planar environment is essential. In order to address these questions, we investigate the electronic structure of Sr$_2$CuO$_3$ and Ni doped Sr$_2$CuO$_3$ single crystals containing (Cu/Ni)O$_4$ square planar units. Our polarization dependent X-ray absorption spectroscopy experiments for Ni in Sr$_2$Cu$_{0.9}$Ni$_{0.1}$O$_3$ have revealed very large orbital polarization, which is a characteristic feature of high $T_c$ cuprate. This arises due to the low spin $S$=0 configuration with two holes in Ni 3$d_{x^2-y^2}$ orbitals - in contrast to the expected high spin $S$=1 state from Hund's first rule. The presence of such $S$=0 Ni$^{2+}$ in hole doped nickelate would be analogous to the Zhang Rice singlet. However, the Mott Hubbard insulating nature of the NiO$_4$ unit would point towards a different electronic phase space of nickelates, compared to high $T_c$ cuprates.
We study the effect of impurities on the two types of spin-dimers in the hybrid chain/ladder spin 1/2 quantum magnet Sr$_{14}$Cu$_{24}$O$_{41}$. Four different impurities were used, namely, the non-magnetic Zn (0.0025 and 0.01 per Cu) and Al (0.0025 and 0.01 per Cu), and magnetic Ni (0.0025 and 0.01 per Cu) and Co (0.01, 0.03, 0.05 and 0.1 per Cu). These impurities were doped in high-quality single-crystals synthesized by the floating zone method. The magnetic susceptibility of pristine Sr$_{14}$Cu$_{24}$O$_{41}$ is analyzed rigorously to confirm that at low temperatures (T $<$ 5 K), the "free" spins in the chains undergo a long-distance dimerization as proposed in a recent study [Sahling et al. Nature Phys., \textbf11, 255 (2015)]. The effect of impurity on these dimers is analyzed by measuring the specific heat down to T = 0.06 K. We found that even at the lower impurity concentration, the long-distance dimers are significantly severed, but the quantum entangled spin dimerized state of the chains persists. On the other hand, the other type of spin dimers that forms at relatively higher temperatures via an intervening Zhang-Rice singlet are found to be practically unaffected at the lower impurity concentration; but at 1\% doping, even these are found to be considerably severed. The effect of Co impurity turned out to be most unusual displaying a strongly anisotropic response, and with a dimerization gap that suppresses faster along the chain/ladder direction than perpendicular to it as a function of increasing Co concentration.
Yannic Utz, Franziska Hammerath, Roberto Kraus, Tobias Ritschel, Jochen Geck, Liviu Hozoi, Jeroen van den Brink, Ashwin Mohan, Christian Hess, Koushik Karmakar, Surjeet Singh, Dalila Bounoua, Romuald Saint-Martin, Loreynne Pinsard-Gaudart, Alexandre Revcolevschi, Bernd Buechner, Hans-Joachim Grafe 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 $S\neq0$.
We study the effect of non-magnetic Zn$^{2+}$ (spin-$0$) and magnetic Ni$^{2+}$ (spin-$1$) impurities on the ground state and low-lying excitations of the quasi-one-dimensional spin-$1/2$ Heisenberg antiferromagnet Sr$_{2}$CuO$_{3}$ using inelastic neutron scattering, specific heat and bulk magnetization measurements. We show that 1 \% Ni$^{2+}$ doping in Sr$_2$CuO$_3$ results in a sizable spin gap in the spinon excitations, analogous to the case of Ni-doped SrCuO$_2$ previously reported [ref. 1]. However, a similar level of Zn$^{2+}$ doping in SrCuO$_2$, investigated here for comparison, did not reveal any signs of a spin gap. Magnetic ordering temperature was found to be suppressed in the presence of both Zn$^{2+}$ and Ni$^{2+}$ impurities, however, the rate of suppression due to Ni$^{2+}$ was found to be much more pronounced than for Zn$^{2+}$. Effect of magnetic field on the ordering temperature is investigated. We found that with increasing magnetic field, not only the magnetic ordering temperature gradually increases but the size of specific heat anomaly associated with the magnetic ordering also progressively enhances, which can be qualitatively understood as due to the field induced suppression of quantum fluctuations.
We investigated the magnetic ground state and low-energy excitations of the spin chains compounds SrCuO$_{2}$ (zigzag chains) and Sr$_{2}$CuO$_{3}$ (linear chains) in the presence of quantum impurities induced by lightly doping ($\leq 1 \%$) with Zn$^{2+}$ ($S = 0$), Co$^{2+}$ ($S =1/2$) and Ni$^{2+}$ ($S = 1$) impurities at the Cu$^{2+}$ site. We show that the ground states and the nature of low-lying excitations (i.e., gapped or gapless) depend on the spin state and symmetry of the defects. For Ni doped chains a spin gap is observed but for Zn and Co doping the excitations remain gapless. Co-doped chains exhibit magnetic order with critical temperatures significantly enhanced compared to those of the pristine compounds. In the specific case of 1 \% Co impurities, the linear chains exhibit long-range order below 11 K, while the zigzag chain is characterized by a quasi-long range ordered phase below 6 K with correlation lengths of about 12\textita and 40\textitc units along the crystal axes \textita and \textitc, respectively. The different magnetic behaviours of these two compounds with comparable intra- and interchain couplings underpin the role of spin frustration in the zigzag chains.
We studied the finite-size effects on the magnetic behavior of the quasi-one-dimensional spin S = $\frac{1}{2}$ Heisenberg antiferromagnets Sr$_{2}$CuO$_{3}$, Sr$_{2}$Cu$_{0.99}$M$_{0.01}$O$_{3}$ (M = Zn and Ni), and SrCuO$_{2}$. Magnetic susceptibility data were analyzed to estimate the concentration of chain-breaks due to extrinsically doped defects and/or due to slight oxygen off-stoichiometry. We show that the susceptibility of Sr$_{2}$Cu$_{0.99}$Ni$_{0.01}$O$_{3}$ can be described by considering Ni$^{2+}$ as a scalar defect ($S_{eff}=0$) indicating that the Ni spin is screened. In Sr$_{2}$Cu$_{0.99}$Zn$_{0.01}$O$_{3}$ susceptibility analysis yields a defect concentration smaller than the nominal value which is in good qualitative agreement with crystal growth experiments. Influence of doping on the low-temperature long-range spin ordered state is studied. In the compound SrCuO$_{2}$, consisting of zigzag S = $\frac{1}{2}$ chains, the influence of spin frustration on the magnetic ordering and the defect concentration determined from the susceptibility data is discussed.
We report on the crystal growth of the quasi one-dimensional quantum spin chain compound SrCuO$_{2}$ and its doped variants containing magnetic cobalt (0.25%, 0.5%, 1% and 2.5%) and non-magnetic zinc (0.5\% and 1\%) impurities. Crystals are grown using the travelling solvent floating zone (TSFZ) method in a four-mirror optical furnace. Some crucial factors, key to the stability of a TSFZ process, including the choice of solvent composition and its associated melting behavior, are discussed in detail. The grown crystals were characterized using x-ray powder diffraction, scanning electron microscopy, optical microscopy, neutron single crystal diffraction and magnetic susceptibility measurements. Co-doping induces magnetic anisotropy and a corresponding change of magnetic behavior characterized by the presence of a sharp peak in the magnetic susceptibility at low-temperatures (T = 5 K), which is not seen for the pristine compound. The peak position is shown to scale linearly with Co-concentration for low doping levels upto 2.5%.