Evolution of the Magnetic Ground States with Lattice Distortion and Chemical Inhomogeneity in Doped Perovskite Oxides

Abstract

The physics of doped transition metal perovskite has been an area of intense research in the last few decades due to their interesting magnetic and transport properties. Various exciting phenomena such as, colossal magneto resistance, high Tc superconductivity, multiferroicity, ferroelectricity, high temperature ferromagnetism, etc., have made these systems more fascinating in terms of fundamental study as well as technological applications. There are several intrinsic material characteristics in these perovskite oxides that can impact their magnetic properties. Lattice distortion and chemical in homogeneity are two important ones. Changes in valence and ionic radius in rare earth (A- site) and transition metal (B- site) directly result in structural modification through internal pressure. Consequently, atomic distances and bond angles between the transition metals vary. This, intern, influences the nearest neighbour exchange coupling energy and magnetic interaction. A detailed investigation has been carried out on two A-site doped perovskite namely, La0.85Sr0.15CoO3 & La0.5Sr0.5CoO3 and two B-site doped perovskite, LaMn0.5Co0.5O3 & LuMn0.5Ni0.5O3 with a view to study the impact of chemical in homogeneity and lattice distortion on their respective magnetic ground states. The thesis is organized in seven chapters. A brief summary of each is given below: Chapter 1: Provides a brief introduction about the perovskite structure. Origins of lattice distortions and its effect on the magnetic properties are discussed. It includes a discussion on different types of indirect magnetic interactions involved in perovskite oxide structure. The chapter concludes with a description of spin-glass, phase separation/ cluster-glass, memory effect in glassy magnetism, critical behaviour at phase transition and specific heat in magnetic systems. Chapter 2: This chapter outlines basic principles of the experimental techniques employed for the work presented in this thesis. Chapter 3: Details macroscopic as well as microscopic investigations carried out to understand the glassy magnetic anomalies in La0.85Sr0.15CoO3 samples. The origin of phase separation (PS) has been reinvestigated. Since the magnetic behavior of La0.85Sr0.15CoO3 (LSCO15) lies in the border of spin glass (SG) and ferromagnetic (FM) region in the x-T phase diagram, it is subject to controversial debate for the last several years. While some research groups favour PS, others regard SG behaviour as the dominant phenomenon. In-depth investigation carried out to elucidate these views is outlined in this chapter in two sections. The first section deals with the glassy magnetic anomalies in single crystals of LSCO15 grown by optical floating zone method. Since the sample crystallizes from melt, it possesses good compositional homogeneity and the phase purity is confirmed by XRD pattern. Many characteristics of canonical SG systems are discernible in the magnetic study, such as, kink in field-cooling curve below Tf, frequency-dependent peak shift and the time dependent memory effect. The relaxation time in sub-pico second range (~10-13 s) is very similar to that of the typical SG systems. Time dependent transport relaxation study exhibits memory effect and the time evolution of resistance scales with magnetization and strictly adheres to the stretched exponential behaviour as commonly expected for a SG-like disordered system. However, a detailed study on transport mechanism and temperature-dependent inverse susceptibility reveals the existence of nanoscopic PS in the sample. In the second section, the origin of PS has been examined through a comprehensive study on two sets of LSCO15 polycrystalline samples prepared from the same initial mixture but subjected to different heat treatment processes. This study depicts the dependence of PS on the preparation conditions. The contrasting magnetic behaviour of PS and SG was resolved by experiments of dc magnetization, linear & non-linear ac susceptibility, neutron depolarization and field-cooled magnetic relaxation. Both samples conform to the general characteristics of a glassy behaviour: a kink in FC magnetization, frequency-dependent peak shift (Vogel–Fulcher law), dc bias-dependent peak shift in accordance with de Almeida–Thouless relation, and characteristic relaxation time in the range of 10-13/10-14 s. This is despite their internal spin structure and interaction being much different at a microscopic level. It is found that the sample processed through a proper homogenization process mimics the SG behaviour, whereas the sample prepared by the conventional method behaves like the PS phase. It is confirmed from neutron depolarization experiments that no ferromagnetic correlation exists in the SG phase of La0.85Sr0.15CoO3, a result in contrast to that of PS phase. Higher harmonic ac susceptibility measurement complements the above observation by the evidence that of 2nd order harmonics are not present in the SG phase of La0.85Sr0.15CoO3. The field-cooled magnetic relaxation study makes a distinct reference to the relaxation process and the strength of interaction between PS and SG like phases. In essence, a concerted effect is made to identify and resolve the spin-glass phase from phase-separated/ cluster-glass. This work shows that chemical in homogeneity is a key factor responsible for phase separation in La0.85Sr0.15CoO3; also intrinsic differences between PS and SG are identified that can serve as guiding tools for research in other similar magnetic oxide systems. It is concluded that the true ground state magnetic property of La0.85Sr0.15CoO3 is spin-glass in nature. Chapter 4: This chapter contains two sections. In the first part, the origin of the re-entrant spin-glass (RSG) behaviour in La0.5Sr0.5CoO3 has been investigated using the conventional magnetometer measurements. Polycrystalline samples prepared by the conventional solid-state synthesis exhibit RSG characteristics with a glassy transition at 190 K. The nature of frequency dependence of χ″(T), a pronounced memory effect and the sluggish response in dc magnetization measurement, all of which clearly indicate the re-entrant behaviour. But, once the sample is taken through a rigorous homogenization procedure of repeated grinding and annealing, its phase turns into pure ferromagnetic one. During the course of this homogenization process, the sample loses oxygen with concurrent degeneration of TC to a lower level. In order to regain the oxygen stoichiometry, it is necessary to anneal the sample in oxygen environment at 900 oC, which triggers deleterious ageing effect by which TC falls progressively with time. In the second part, the effect of oxygen stoichiometry on La0.5Sr0.5CoO3 (LSCO50) thin-films has been investigated. The highest TC reported so far for LSCO50 thin film is 250 K, which is significantly less compared to the bulk TC (262 K) of an oxygen stoichiometric compound. This work focuses on achieving the highest ferromagnetic transition temperature (TC) for LSCO50 films under optimized growth conditions. The analysis of experimental data suggests that the Curie temperature can be enhanced to 262 K, irrespective of whether or not, (a) the film on LAO or STO or (b) any induced strain occurs in the LSCO50 film. Apart from different thin-film growth parameters such as oxygen pressure and substrate temperature during the growth, and post-growth annealing temperature and oxygen pressure, the profile of the laser beam used for ablation of bulk material profile also plays an important role. The elevation of Curie temperature observed in thin-films to that close to the bulk value is believed to be a result of improved stoichiometric composition of oxygen facilitated during thin film growth. However, the strong ageing effect seen is quite close to that is observed in oxygen-annealed polycrystalline sample. Chapter 5: Of the three segments constituting this chapter, the first outlines different magnetic anomalies induced by lattice distortion in LaMn0.5Co0.5O3 (LMCO) single crystals. Single crystals of LMCO compound [(100) orientation] have been successfully grown using the optical floating zone method. Powder as well as single crystal x-ray diffraction analyses provides evidence of large strain dependent structural distortion in as-grown crystals. Spatially resolved 2-D Raman scan reveals that the strain generates a distribution of octahedral distortion in the lattice. While some are compressive in nature, others in the nearby territory relate to tensile distortion. The ac susceptibility measurement elucidates distinct changes in the ferromagnetic transition temperature (TC) in the as grown (strained) crystal. It is possible to release strain by rigorous annealing process. Which also results in a uniform TM-O octahedral deformation. Room temperature 2-D Raman spectra bears testimony to this. Upon annealing, the single crystalline order is diminuend by the atomic rearrangement. This causes tilting of the oxygen octahedra, by decreasing intra-octahedral angle θTM-O-TM, and lowering of exchange energy Jex between the magnetic ions. The transition temperature falls and the magnetic phase merges with that in the strain-free polycrystalline material. A detailed critical analysis performed in the vicinity of paramagnetic to ferromagnetic phase transition in both the samples establishes that the ground state magnetic behaviour, assigned to the strain-free LMCO crystal is of 3D Heisenberg type. But the local octahedral distortion present in the as-grown crystal causes mean field like magnetic interaction at few local sites. This serves as a key drive for the critical exponents to distance from the 3D Heisenberg model towards the mean-field type. The second part of this chapter concerns the anomalous re-entrant glassy magnetic behaviour observed in LMCO single crystals. The ac susceptibility study illustrates the low temperature anomalous glassy magnetic ordering in these crystals. The material behaves like a normal magnetic glass, (frequency-dependent peak-shift in ac susceptibility) in conformance with the phenomenological Vogel-Fulcher law, of spin flips time: ~10-4 s. However, the crystal does not respond to the external dc bias and just as well remains free from memory effect. Anomalous behaviour of this kind is rare in magnetic oxides. The magneto-dielectric effect in LMCO is discussed in the third section of this chapter. The real part of dielectric permittivity (ε′) has a colossal value of 1800 at 220 K and 10 kHz. However as the sample is cooled further, ε′ decreases slowly; followed by dielectric relaxation in the region, 120 - 150 K. Detailed analysis of the temperature dependence of the imaginary part of the dielectric permittivity (ε″) show that there is no relaxor-like phenomena in this compound. The frequency dependence of ε″ reveals that the low frequency region is dominated by Maxwell-Wagner relaxation, whereas, at high frequency, a Debye type relaxation persists. The temperature dependent full-width at half-maximum for this Debye relaxation, peaks at the corresponding TC. The temperature variation of the relaxation time has two domains of different slopes. At zero external field, ε″(ω) has a low activation energy (U = 46.4 meV) in the ferromagnetic region, compared to that in the paramagnetic (60.1 meV) phase. The boundary lies near the corresponding TC. In the presence of external applied field 5 T, U remains unchanged in the ferromagnetic region, but decreases ( U ~ 5 meV) in the paramagnetic phase. These results signify the existence of strong magneto-dielectric coupling in LMCO crystals. The field variation of ε′(ω) at fixed temperature and specific frequency highlights the rise in magnetodielectricity (MD) as well as magneto-loss (ML) with increasing magnetic field. It is perceived that this variation is not due to the magneto resistance of LMCO or caused by LMCO - electrode interfaces. The influence of extrinsic parasitic contributions cannot be ruled out entirely, but the presence of positive MD as well as ML at frequencies above the time constant suggests that the relaxation process and the magneto-dielectric coupling are intrinsic to the LaMn0.5Co0.5O3 system. Chapter 6: This chapter describes the successful synthesis of a new perovskite oxide compound, LuMn0.5Ni0.5O3. The structural characterization employs the Rietveld refinement of powder X-ray diffraction pattern. The compound crystallizes in orthorhombic Pbnm crystal structure. dc magnetization reveals ferromagnetic ordering in the sample. However the low temperature glassy phase spotted in the ac susceptibility measurement might classify it as a re-entrant spin-glass compound. But the display of memory effect until the ferromagnetic transition indicates that intrinsic ant ferromagnetic interaction prevails over the dominant ferromagnetic interaction. A critical behaviour study was carried out in the vicinity of the ferromagnetic to paramagnetic phase transition, which provided the critical exponents: α = 0.37, β = 0.241 ± 0.003, γ = 1.142 ± 0.003 and δ = 5.77 ± 0.03. Interestingly, this set of critical exponents does not match with any of the conventional theories of mean field, 3D Heisenberg, and 3D Ising. Rather it fits quite well with data calculated for the stacked triangular 3D version of the (Z2 × S1) model [α = 0.34 ± 0.06, β = 0.25 ± 0.01, γ = 1.13 ± 0.05 and δ = 5.47 ± 0.27]. This study indicates that the magnetic ground state of LuMn0.5Ni0.5O3 is canted ferromagnetic. Chapter 7: Various important results are summarized in this chapter. It also provides a broad outlook in this area of research.