Manganite Films Research Articles

Magnetic Circular Dichroism of Oxide Films: Study of Electronic, Magnetic and Charge States

Semiconductor materials based on ZnO and RE3+MnO3 oxides are considered as potential candidates for spintronics. This article presents the methodology and results of studying the effect of magnetic circular dichroism for Zn1-xCoxO, Zn1-x-yCoxAlyO and RE1-x 3+Ax 2+MnO3 film structures in the visible radiation range. It has been shown that the magnetic circular dichroism behavior of the manganite films reflects not only the magnetic, but also the charge component of the material. This indicates the possibility of studying the magnetic and transport characteristics of the films using the magnetic circular dichroism spectroscopy. Since the magnetic circular dichroism effect also directly probes the ground and excited electronic states of the film, it has been obtained data that update calculated parameters for describing the manganites band structure. In the case of the Zn1-xCoxO and Zn1-x-yCoxAlyO films, the magnetic circular dichroism spectroscopy acts as a tool for detecting Co nanoparticles in the solid solution matrix of ZnO:Co and ZnO:(Co+Al).

Preparation of Atomically Smooth SrTiO₃ Substrates

SrTiO3 has been used as a substrate to grow thin films of materials including high-temperature superconductors such as cuprates, ferromagnetic oxides such as manganites, and ferroelectric oxides such as BaTiO3. The use of SrTiO3 as a substrate for the deposition of manganite thin films provides an excellent template for observing unique effects observed only in ferromagnets, such as the anomalous and planar Hall effects. The as-received SrTiO3 substrates require a process that prepares atomically smooth surfaces for thin film deposition. This study focuses on using ultrasonic cleaning, water annealing, and thermal annealing in air to prepare SrTiO3 substrate surfaces and verifying their smoothness at the atomic scale using atomic force microscopy.

The visible magneto-optical response of RE1-xAxMnO3manganites: relationship with the charge component of the material.

Magnetic circular dichroism (MCD) spectroscopy for manganite films of various compositions and morphologies has been studied in the range of 1.2-3.7 eV. The primary focus was on the temperature behavior of the MCD spectra, as well as the magnetization and resistivity of the films. The data obtained were analyzed in comparison with magneto-optical spectroscopy of the Kerr rotation (KR) on both single crystal and thin film of manganites. It has been established that the MCD response at 2.3 eV is typical for manganites transitioning into a conducting state. Consequently, it reflects a change in the band structure of the material. This response is also observed in the KR spectrum of manganites in the range 2.3-2.6 eV below the metal-insulator transition temperature. These findings complement the understanding of the electronic structure of manganites in general. Moreover, they also provide a basis for the search for new functional materials.

Manganite memristive devices: recent progress and emerging opportunities

Manganite-based memristive devices have emerged as promising candidates for next-generation non-volatile memory and neuromorphic computing applications, owing to their unique resistive switching behavior and tunable electronic properties. This review explores recent innovations in manganite-based memristive devices, with a focus on materials engineering, device architectures, and fabrication techniques. We delve into the underlying mechanisms governing resistive switching in manganite thin films, elucidating the intricate interplay of oxygen vacancies, charge carriers, and structural modifications. This review underscores breakthroughs in harnessing manganite memristors for a range of applications, from high-density memory storage to neuromorphic computing platforms that mimic synaptic and neuronal functionalities. Additionally, we discuss the role of characterization techniques and the need for a unified benchmark for these devices. We provide insights into the challenges and opportunities associated with the co-integration of manganite-based memristive devices with more mature technologies, offering a roadmap for future research directions.

Nuclear and magnetic structure of an epitaxial La0.67Sr0.33MnO3 film using diffraction methods

We use a combination of transmission electron microscopy, X-ray and neutron diffraction, Superconducting Quantum Interference Device (SQUID) magnetometry and symmetry analysis to determine the nuclear and magnetic structure of an epitaxial La0.67Sr0.33MnO3 film, deposited on a Si substrate. The film undergoes a magnetic ordering transition at 260 K. At 300 K, in the paramagnetic phase, the manganite film has a I4/m space group. In the magnetic phase, SQUID and neutron diffraction results lead us to assign a ferromagnetic spin-order to the film, associated to magnetic moments with a slightly out-of-plane component, namely (3.5,0,0.3)μB. Symmetry analysis further shows that only the P1̄′ group is compatible with such a magnetic ordering.

Relationship between structure and charge/orbital order in epitaxial single layer Ruddlesden–Popper manganite thin films

Relationship between structure and charge/orbital order in epitaxial single layer Ruddlesden–Popper manganite thin films

Boosting ferromagnetism in freestanding electronically phase separated manganite thin films

Boosting ferromagnetism in freestanding electronically phase separated manganite thin films

Magnetic proximity sensor based on colossal magnetoresistance effect

Magnetic proximity sensors are widely used to determine the distance to ferromagnetic or highly conductive materials and to investigate their shape or to detect their motion. In this study, a magnetic proximity sensor incorporating a cylindrical permanent magnet and a scalar magnetic field sensor (measuring the magnitude of the field independently from its orientation) based on the phenomenon of colossal magnetoresistance in manganite films is presented. Two versions of the sensor, one with a solid cylindrical magnet and one with a hollow cylindrical magnet, were constructed and tested. A steel plate and a superconducting YBaCuO disk were used to investigate the static response. The measurements of the dynamic behavior were carried out with rotating steel and duralumin plates. The results of the static experiments and modelling showed that the output response (change of the magnetic field) of the sensor had a hyperbolic relationship with the distance between the sensor and the measured object. This change was positive for solid cylindrical magnet design and negative for hollow cylindrical magnet design when the target was steel. In contrast, the solid magnet-based sensor produced a negative signal for the superconducting material, while the hollow cylindrical magnet sensor showed a positive signal. It was found that the main features of the dynamic response of the proximity sensors can be explained by the magnetization of steel and the induction of eddy currents in duralumin. The present study demonstrates that the proposed magnetic proximity sensor can be successfully used to search for ferromagnetic objects, investigate the properties of superconductors and detect the motion of non-ferromagnetic conductive materials and can have advantages over conventional magnetic proximity sensors.

Scalable and environmentally friendly production of perovskite manganite thin films for neuromorphic applications

A method of producing high-quality thin films of perovskite manganites utilizing citrate-based aqueous chemical solution deposition is presented. The method is applied to the production of thin films of gadolinium calcium manganite, Gd1−xCaxMnO3 (GCMO). The film quality is verified by x-ray diffraction analysis, electron microscopy, and magnetic measurements. Finally, planar memristors are fabricated using GCMO films, demonstrating the material’s ability to exhibit resistive switching. This underscores its potential for future memristor technologies.

Magnetic Interactions with Strain Gradient in Ultrathin Pr0.67Sr0.33MnO3 Films

Strain gradient is a normal phenomenon around a heterostructural interface in ultrathin film, and it is important to determine its effect on magnetic interactions to understand interfacial coupling. In this work, ultrathin Pr0.67Sr0.33MnO3 (PSMO) films on different substrates are studied. For PSMO film under different in-plane strain conditions, the saturated magnetization and Curie temperature can be qualitatively explained by double-exchange interaction and the Jahn–Teller distortion. However, the difference in the saturated magnetization with zero field cooling and 5 T field cooling is proportional to the strain gradient. Strain-gradient-induced structural disorder is proposed to enhance phonon–electron antiferromagnetic interactions and the corresponding antiferromagnetic-to-ferromagnetic phase transition via a strong magnetic field during the field cooling process. A non-monotonous structural transition of the MnO6 octahedral rotation can enlarge the strain gradient in PSMO film on a SrTiO3 substrate. This work demonstrates the existence of the flexomagnetic effect in ultrathin manganite film, which should be applicable to other complex oxide systems.

A study on the kinetic arrest of magnetic phases in nanostructured Nd0.6Sr0.4MnO3 thin films

The Nd0.6Sr0.4MnO3 (NSMO) manganite system exhibits a phase transition from paramagnetic insulating (PMI) to ferromagnetic metallic (FMM) state around its Curie temperature T C = 270 K (bulk). The morphology-driven changes in the kinetically arrested magnetic phases in NSMO thin films with granular and crossed-nano-rod-type morphology are studied. The manganite thin films at low temperatures possess a magnetic glassy state arising from the coexistence of the high-temperature PMI and the low-temperature FMM phases. The extent of kinetic arrest and its relaxation was studied using the ‘cooling and heating in unequal field (CHUF)’ protocol in magnetic and magnetotransport investigations. The sample with rod morphology showed a large extent of phase coexistence compared to the granular sample. Further, with a field-cooling protocol, time-evolution studies were carried out to understand the relaxation of arrested magnetic phases across these morphologically distinct thin films. The results on the devitrification of the arrested magnetic state are interpreted from the point of view of homogeneous and heterogeneous nucleation of the ferromagnetic phase in the paramagnetic matrix with respect to temperature.

Influence of crystallographic orientation on electronic phase separation in manganite thin films

Thin film epitaxy is a powerful method to control the strain and crystallographic orientation of the thin films using epitaxial relationship with the substrate. For colossal magnetoresistive (CMR) manganites thin films, the strong correlation between spin, charge, orbital and lattice degrees of freedom make their physical properties depend sensitively on the choice of substrate. This is especially true when considering the fact that the physical behaviors of manganites are often governed by electronic phase separation (EPS) phenomena, whose physical origin is strongly tied to lattice strain distribution. While many studies have been conducted on the substrate lattice mismatch induced strain effect, research on the substrate crystallographic orientation effect on EPS has received less attention. In this work, using (La2/3Pr1/3)5/8Ca3/8MnO3 (LPCMO) films grown on SrTiO3 (STO) substrate as a protype system, we show that EPS and its associated physical properties are strongly affected by the substrate crystallographic orientations. Specifically, we observed a clear boost of ferromagnetism in (110)-oriented LPCMO thin films with elongated EPS domains. First principles calculations show that the magnetic phase transitions of LPCMO are dominantly influenced by the spin-lattice coupling.

Strain-induced phase transition at the surface of epitaxial La0.65Sr0.35MnO3 films

The strong coupling between lattice, electron and spin systems in perovskite manganites along with symmetry breaking at interfaces could lead to inherently different electronic and structural phases at the surface of thin manganite films. To study whether the surface reconstruction can be tuned by epitaxy strain, we employed Surface-Enhanced Raman Spectroscopy (SERS) on La0.65Sr0.35MnO3 (LSMO) thin films epitaxially grown on LaAlO3 substrates. A moderate compressive strain (ε < 1 %) did not change the surface state as compared to that found in unstrained LSMO/MgO(200) films. In contrast, a strong in-plane compressive strain (2 < ε < 3.4 %) stabilizes a novel phase at the surface, characterized by a unique SERS spectrum, which reveals a phase transition at T* = 220 K accompanied by an anomalously strong hardening of the Jahn-Teller mode.

Fully Magnetically Polarized Ultrathin La0.8Sr0.2MnO3 Films.

We report the observation of fully magnetically polarized ultrathin La0.8Sr0.2MnO3 films by using LaMnO3 and La0.45Sr0.55MnO3 buffer layers grown epitaxially on SrTiO3(001) substrates by molecular beam epitaxy. Specifically, we show that La0.8Sr0.2MnO3 films grown on 12-unit-cell LaMnO3 have bulk-like magnetic moments starting from a single unit cell thickness, while for the 15-unit-cell La0.45Sr0.55MnO3 buffer layer, the La0.8Sr0.2MnO3 transitions from an antiferromagnetic state to a fully spin-polarized ferromagnetic state at 4 unit cells. The magnetic results are confirmed by X-ray magnetic circular dichroism, while linear dichroic measurements carried out for the La0.8Sr0.2MnO3/La0.45Sr0.55MnO3 series show the presence of an orbital reorganization at the transition from the antiferromagnetic to ferromagnetic state corresponding to a change from a preferred in-plane orbital hole occupancy, characteristic of the A-type antiferromagnetic state of La0.45Sr0.55MnO3, to preferentially out of plane. We interpret our findings in terms of the different electronic charge transfers between the adjacent layers, confined to the unit cell in the case of insulating LaMnO3 and extended to a few unit cells in the case of conducting La0.45Sr0.55MnO3. Our work demonstrates an approach to growing ultrathin mixed-valence manganite films that are fully magnetically polarized from the single unit cell, paving the way to fully exploring the unique electronic properties of this class of strongly correlated oxide materials.

Effects of electric field and light on resistivity switching of Eu0.7Sr0.3MnO3 thin films.

Based on the excellent piezoelectric properties of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 (PMN-PT) single crystals, a hole-doped manganite film/PMN-PT heterostructure has been constructed to achieve electric-field and light co-control of physical properties. Here, we report the resistivity switching behavior of Eu0.7Sr0.3MnO3/PMN-PT(111) multiferroic heterostructures under different in-plane reading currents, temperatures, light stimuli and electric fields, and discuss the underlying coupling mechanisms of resistivity change. The transition from the electric-field induced lattice strain effect to polarization current effect can be controlled effectively by decreasing the in-plane reading current at room temperature. With the decrease of temperature, the interfacial charge effect dominates over the lattice strain effect due to the reduced charge carrier density. In addition, light stimulus can lead to the delocalization of eg carriers, and thus enhance the lattice strain effect and suppress the interfacial charge effect. This work helps to understand essential physics of magnetoelectric coupling and also provides a potential method to realize energy-efficient multi-field control of manganite thin films.

Polarization-dependent photoinduced metal–insulator transitions in manganites

In correlated oxides, collaborative manipulation on light intensity, wavelength, pulse duration and polarization has yielded many exotic discoveries, such as phase transitions and novel quantum states. In view of potential optoelectronic applications, tailoring long-lived static properties by light-induced effects is highly desirable. So far, the polarization state of light has rarely been reported as a control parameter for this purpose. Here, we report polarization-dependent metal-to-insulator transition (MIT) in phase-separated manganite thin films, introducing a new degree of freedom to control static MIT. Specifically, we observed giant photoinduced resistance jumps with striking features: (1) a single resistance jump occurs upon a linearly polarized light incident with a chosen polarization angle, and a second resistance jump occurs when the polarization angle changes; (2) the amplitude of the second resistance jump depends sensitively on the actual change of the polarization angles. Linear transmittance measurements reveal that the origin of the above phenomena is closely related to the coexistence of anisotropic micro-domains. Our results represent a first step to utilize light polarization as an active knob to manipulate static phase transitions, pointing towards new pathways for nonvolatile optoelectronic devices and sensors.

Tilted Magnetic Anisotropy with In‐Plane Broken Symmetry in Ru‐Substituted Manganite Films

AbstractControlling the magnetic anisotropy of materials is important in a variety of applications including magnetic memories, spintronic sensors, and skyrmion‐based devices. Ru‐substituted La0.7Sr0.3MnO3 (Ru‐LSMO) is an emerging material, showing tilted magnetic anisotropy (TMA) and possible nontrivial magnetic topologies. Here anisotropic in‐plane magnetization is reported in moderately compressed Ru‐LSMO films, coexisting with TMA. This combination is attractive for technological applications, such as spin‐orbit torque (SOT) based devices and other spintronic applications. A microstructural analysis of films of this material is presented, and Ru single ion anisotropy and strain‐induced structural mechanisms are found to be responsible for both the in‐plane anisotropy and the TMA. The manifestation of these properties in a correlated oxide with Curie temperature near room temperature highlights an attractive platform for technological realization of SOT and other spintronic devices. Illustrating the mechanisms behind these properties provides the necessary engineering space for harnessing these phenomena for practical devices.

High room temperature magnetoresistance in La0.9Sr0.1Mn1-yZnyO3 epitaxial films

Developing large room temperature magnetoresistance materials has been a major hotspot for a few last decades due to its importance in the practical applications in magneto-resistive random access memory, and it remains a challenge. Here, La0.9Sr0.1Mn1-yZnyO3 (LSMZO) films have been grown on SrTiO3 substrates by magnetron sputtering, showing excellent quality of epitaxy. Upon increasing Zn content, the reduction of Curie temperature (TC) and metal-insulator transition temperature (TMI) is observed, accompanied by the increase of coercive field and room-temperature resistivity. Analysis on the fraction of Mn3+ and Mn4+ indicates that Zn2+ substitution at Mn site results in a higher Mn4+ fraction departing from the optimum value and hence a weaker double-exchange interaction by replacing more Mn3+. Besides that, ionic radius mismatch induced internal strain and substrate induced tensile strain also play a part. Most significantly, the enhanced magnetic disorder gives rise to an increase of intrinsic magnetoresistance around room temperature in LSMZO (y = 10%) film, and a large magnetoresistance of 18.4% is obtained under 0.3 T at 280 K in this sample. Our research provides a simple and effective approach to achieve a large room temperature magnetoresistance in Mn site doped manganite epitaxial films.

Enhanced temperature coefficient of resistance in nanostructured Nd0.6Sr0.4MnO3 thin films

Manganite thin films are promising candidates for studying strongly correlated electron systems. Understanding the growth and morphology-driven changes in the physical properties of manganite thin films is vital for their applications in oxitronics. This work reports the morphological, structural, and electrical transport properties of nanostructured Nd0.6Sr0.4MnO3 thin films fabricated using the pulsed laser deposition technique. Scanning electron microscopy imaging of the thin films revealed two prominent surface morphologies: a granular and a crossed-nano-rod-type morphology. From X-ray diffraction and atomic force microscopy analysis, we found that the observed nanostructures resulted from altered growth modes on the terraced substrate surface. Furthermore, investigations on the electrical-transport properties of thin films revealed that the films with crossed-nano-rod morphology showed a sharp resistive transition near the metal-to-insulator transition. Also, an enhanced temperature coefficient of resistance (TCR) of up to one order of magnitude was observed compared to the films with granular morphology. Such enhancement in TCR% by tuning the morphology makes these thin films promising candidates for developing oxide-based temperature sensors and detectors.

Improper ferroelectricity in ultrathin hexagonal ferrites films

Suppression of ferroelectricity in ultrathin films of improper ferroelectric hexagonal ferrites or manganites has been attributed to the effect of interfacial clamping; however, the quantitative understanding and related phenomenological model are still lacking. In this work, we report on the paraelectric-to-ferroelectric phase transition of epitaxial h-ScFeO3 films with different thicknesses through in situ reflection high-energy electron diffraction. Based on the interfacial clamping model and the Landau theory, we show that the thickness-dependence of the ferroelectric Curie temperature can be understood in terms of the characteristic length of an interfacial clamping layer and the bulk Curie temperature. Furthermore, we found that the critical thickness of improper ferroelectricity is proportional to the characteristic length of the interfacial clamping layer. These results reveal the essential role of mechanical clamping from interface on the improper ferroelectricity of hexagonal ferrites or manganites and could serve as the guidance to achieve robust improper ferroelectricity in ultrathin films.