Magnetism in layered Nickelates and Cobaltates

• Main Author: Drees, Jan Yvo
• Other Authors: Technische Universität Dresden, Fakultät Mathematik und Naturwissenschaften
• Format: Doctoral Thesis
• Language: English
• Published: Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden 2016
• Subjects: Cobaltate; Nickelate; Magnetism; incommensurate; ddc:530; rvk:UP 6800
• Online Access: http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-192533; http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-192533; http://www.qucosa.de/fileadmin/data/qucosa/documents/19253/PhD_Drees.pdf

Single layered perovskites with the chemical formula La2−xSrxTO4 (T = transition metal) exhibit a variety of intriguing ordering phenomena. The most outstanding is the occurrence of high temperature superconductivity in La2−xSrxCuO4, which can be considered as the prototype system for the more complex cuprates. Some cuprates show incommensurate static charge order at low temperatures [38–40]. For others it is believed that charges are dynamically correlated [39, 147, 259]. Such effects are difficult to measure if the charges fluctuate. In contrast to the cuprate La2−xSrxCuO4 the isostructural nickelates and cobaltates remain insulating over a wide doping range [112, 134, 135, 138]. While incommensurate charge stripe order is long known for the nickelates, recently also evidence for charge stripes in cobaltates has been published [174]. Single crystal rods, with ≈10cm length and ≈0.8cm diameter, have been grown by the traveling solvent floating zone technique using an optical four mirror furnace. We investigated strontium doped nickelates in the range 0.15 ≤ x ≤ 0.22. In addition, also co-doped nickelates have been investigated. A large number of samples with different doping concentrations enabled us to systematically characterize the sample properties. Powder X-ray diffraction measurements were used to determine the lattice parameters. For the nickelates we could confirm the doping dependence of the lattice constants reported in literature [202]. The main interest for the cobaltate system was in the strontium doping range 1/3 ≤ x ≤ 1/2. It was previously reported that the ab-lattice parameter exhibits an anomalous peak around a Sr doping x ≈ 1/3 [140]. We could not confirm such an anomaly for our samples and, instead, we observe a strictly monotonic doping dependence of the lattice parameters which we attribute to the close to perfect stoichiometry of our samples. Samples with the 214-layered perovskite structure can be synthesized over a wide range of oxygen off-stoichiometry. However, the oxygen content can have similarly strong influence on the sample properties as strontium doping. It is therefore essential for data interpretation to determine the oxygen off stoichiometry. EDX and WDX measurements were used to confirm the oxygen content in our nickelates to be nearly stoichiometric. The oxygen content determination of the cobaltates is somewhat more difficult. Thermogravimetry measurements in a flow of Ar/H2 confirmed a nearly stoichiometric oxygen content δ in La2−xSrxCoO4+δ for all samples. We used neutron diffraction measurements to determine the magnetic order in our nickelate samples. In stripe ordered nickelates a small titanium co-doping of the order of 5% is suficcient to supress the incommensurate magnetism and restore antiferromagnetic order. Within the series of zinc co-doped nickelates three samples exhibit an incommensurability epsilon ≈ 1/8, indicating the stabilization of an intermediate stripe pattern with an eightfold unit cell. Compared to the epsilon ≈ 1/3 regime the correlation length is greatly reduced. The magnon dispersion of two samples within the intermediate stripe phases with epsilon ≈ 1/8 and epsilon ≈ 1/4 has been measured with neutron spectroscopy. The observed dispersion neither resembles the one in the undoped nor the 1/3 strontium doped samples. Despite the amount of disorder in our co-doped nickelate materials there are no clear signs for the emergence of hourglass spectra which is most likely caused by a strong exchange interaction across the holes. We investigated the charge and magnetic order in the incommensurate regime of La2−xSrxCoO4 with doping 0.33 ≤ x ≤ 0.5 by elastic neutron scattering and hard X-ray synchrotron measurements. In contrast to the established opinion that this phase is characterized by charge stripe order we were able to show that no charge stripes are present. Instead we found that checkerboard charge order, which is most stable at x = 1/2, persists to a much lower doping than previously thought. The absence of charge stripes is also in agreement with the dispersion of the top most Co-O bond stretching phonon mode. Charge order can induce an anomaly in this branch according to the modulation vector ~q. We observed a softening at ~q = (1/2 1/2 0), which is consistent with our expectations for a checkerboard charge ordered phase. Inelastic neutron measurements revealed an additional high energy part of the hourglass dispersion which has not been reported so far. The entire lowenergy spin excitations that belong to the classical hour-glass dispersion are mostly in-plane excitations, the newly discovered high-energy magnon mode arises from out-of-plane excitations. The resemblance between the low energy excitations below the neck of the hourglass with the excitations in La1.5Sr0.5CoO4 and similarly between the high energy excitations with those observed in La2CoO4 suggests that the observed dispersion is not a single dispersion, but instead consists of two dispersions with distinct origin. In this model the low-energy dispersion arises mainly from magnetic excitations of hole doped regions and the high-energy part would be connected to magnetic excitations within the undoped islands. The absence of charge stripe order in the insulating cobaltates in combination with an unmagnetic low spin state for Co+3 requires a different explanation for the presence of incommensurate magnetic order. We propose a picture on the basis of the ideal checkerboard charge order of the half doped reference system. Decreasing the strontium concentration requires the replacement of Co+3 by Co+2, effectively resulting in the competition between the antiferromagnetic order of the undoped and the antiferromagnetic order of the half doped compound. The induced frustration can be released by a twisting of magnetic moments away from their antiferromagnetic orientation, ultimately leading to the observed incommensurate magnetic order.