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A Mn valence instability on La2/3Ca1/3MnO3 thin films, grown on LaAlO3 (001)substrates is observed by x-ray absorption spectroscopy at the Mn L-edge and O K-edge. As-grown samples, in situ annealed at 800 C in oxygen, exhibit a Curie temperature well below that of the bulk material. Upon air exposure a reduction of the saturation magnetization, MS, of the films is detected. Simultaneously a Mn2+ spectral signature develops, in addition to the expected Mn3+ and Mn4+ contributions, which increases with time. The similarity of the spectral results obtained by total electron yield and fluorescence yield spectroscopy indicates that the location of the Mn valence anomalies is not confined to a narrow surface region of the film, but can extend throughout the whole thickness of the sample. High temperature annealing at 1000 C in air, immediately after growth, improves the magnetic and transport properties of such films towards the bulk values and the Mn2+ signature in the spectra does not appear. The Mn valence is then stable even to prolonged air exposure. We propose a mechanism for the Mn2+ ions formation and discuss the importance of these observations with respect to previous findings and production of thin films devices.
The magnetic properties of a series of YBa2Cu3O7-x/La2/3Ca1/3MnO3 (YBCO/LC1/3MO) superlattices grown by dc sputtering at high oxygen pressures (3.5 mbar) show the expected ferromagnetic behaviour. However, field cooled hysteresis loops at low temperature show the unexpected existence of exchange bias, effect associated with the existence of ferromagnetic/antiferromagnetic (F/AF) interfaces. The blocking temperature (TB) is found thickness dependent and the exchange bias field (HEB) is found inversely proportional to the FM layer thickness, as expected. The presence of an AF material is probably associated to interface disorder and Mn valence shift towards Mn4+.
Surface magnetic properties of perovskite manganites have been a recurrent topic during last years since they play a major role in the implementation of magnetoelectronic devices. Magneto-optical techniques, such as X-ray magnetic circular dichroism, turn out to be a very efficient tool to study surface magnetism due to their sensitivity to magnetic and chemical variations across the sample depth. Nevertheless, the application of the sum rules for the determination of the spin magnetic moment might lead to uncertainties as large as 40% in case of Mn ions. To overcome this problem we present an alternative approach consisting of using X-ray magnetic circular dichroism in reflection geometry. Fit of the data by using a computer code based in a 4X4 matrix formalism leads to realistic results. In particular, we show that surface and interface roughness are of major relevance for a proper description of the experimental data and a correct interpretation of the results. By using such an approach we demonstrate the presence of a narrow surface region with strongly depressed magnetic properties in La2/3Ca1/3MnO3 thin films.
The electronic phase separation (EPS) of optimally doped La2/3Ca1/3MnO3 (LCMO) thin films under various degrees of anisotropic strain is investigated by static magnetotransport and dynamic relaxation measurements. Three LCMO films were grown simultaneously on (001) NdGaO3 (NGO) substrates by pulsed laser deposition, and then post-growth annealed at 780 oC in O2 for different durations of time. With increasing annealing time, the films developed significant strains of opposite signs along the two orthogonal in-plane directions. The static temperature-dependent resistivity, R(T), was measured simultaneously along the two orthogonal directions. With increasing annealing time, both zero-field-cooled and field-cooled R(T) show significant increases, suggesting strain-triggered EPS and appearance of antiferromagnetic insulating (AFI) phases in a ferromagnetic metallic (FMM) ground state. Meanwhile, R(T) along the tensile-strained [010] direction becomes progressively larger than that along the compressive-strained [100]. The enhanced resistivity anisotropy indicates that the EPS is characterized by phase-separated FMM entities with a preferred orientation along [100], possibly due to the cooperative deformation and rotation/tilting of the MnO6 octahedra under the enhanced anisotropic strain. The anisotropic EPS can also be tuned by an external magnetic field. During a field-cycle at several fixed temperatures, the AFI phases are melted at high fields and recovered at low fields, resulting in sharp resistance changes of the ratio as high as 104. Furthermore, the resistivity was found to exhibit glass-like behavior, relaxing logarithmically in the phase-separated states. Fitting the data to a phenomenological model, the resulting resistive viscosity and characteristic relaxation time are found to evolve with temperature, showing a close correlation with the static measurements in the EPS states.
Giant Random Telegraph Noise (RTN) in the resistance fluctuation of a macroscopic film of perovskite-type manganese oxide La2/3Ca1/3MnO3 has been observed at various temperatures ranging from 4K to 170K, well below the Curie temperature (TC = 210K). The amplitudes of the two-level-fluctuations (TLF) vary from 0.01% to 0.2%. We use a statistical analysis of the life-times of the TLF to gain insight into the microscopic electronic and magnetic state of this manganite. At low temperature (below 30K) The TLF is well described by a thermally activated two-level model. An estimate of the energy difference between the two states is inferred. At higher temperature (between 60K and 170K) we observed critical effects of the temperature on the life-times of the TLF. We discuss this peculiar temperature dependence in terms of a sharp change in the free energy functional of the fluctuators. We attribute the origin of the RTN to be a dynamic mixed-phase percolative conduction process, where manganese clusters switch back and forth between two phases that differ in their conductivity and magnetization.
The existence of coherent magnetic correlations in the normal phase of cuprate high-temperature superconductors has proven difficult to measure directly. Here we report on a study of ferromagnetic-superconductor bilayers of La2/3Ca1/3MnO3/YBa2Cu3O7 (LCMO/YBCO) with varying YBCO layer thicknesses. Using x-ray magnetic circular dichroism, we demonstrate that the ferromagnetic layer induces a Cu magnetic moment in the adjacent high-temperature superconductor. For thin samples, this moment exists at all temperatures below the Curie temperature of the LCMO layer. However, for a YBCO layer thicker than 12 unit cells, the Cu moment is suppressed for temperatures above the superconducting transition, suggesting this to be a direct measurement of magnetic coherence in the normal state of a superconducting oxide.