LaMnO3 Thin Films Research Articles

Influence of calcination temperature on the 3D nanoscale topography of LaMnO3 thin films: A comprehensive surface analysis

In this paper, we present a comprehensive study on the 3D nanoscale topography of LaMnO3 thin films, focusing on the influence of calcination temperature on surface morphology. The study reveals significant structural, chemical, and morphological changes as a function of the calcination temperature. XRD analysis confirmed the formation of the orthorhombic LaMnO3 structure at 700 °C, 750 °C, and 800 °C, with increasing unit cell volume and crystallite size observed at higher temperatures. FTIR spectra identified characteristic functional groups associated with molecular vibrations, indicating the perovskite structure. SEM imaging showed grain growth with temperature, while EDS analysis confirmed compound formation and substrate interactions. AFM analysis revealed increased surface roughness with temperature, attributed to nucleation and crystal growth. Morphological and microtextural analyses further detailed changes in surface features, peaks, valleys, and voids. Fractal characterization highlighted variations in surface texture with temperature, with a decrease in dominant wavelength indicating changes in microtexture complexity. Overall, the findings provide insights into the temperature-dependent properties of LaMnO3 thin films, essential for optimizing growth conditions and understanding their potential applications in various fields.

Interpretation of complex optical properties and optical transitions of epitaxial LaMnO3 thin films

An in-depth analysis of the optical properties of epitaxial (001) oriented LaMnO3films grown on SrTiO3and LaAlO3single crystal substrates is performed by spectroscopic ellipsometry to determine the complex dielectric function (ε = ε1 + iε2) spectra from 0.12 to 5.89 eV. Density Functional Theory and many body perturbation theory within the G0W0 and the Bethe-Salpeter Equation approximations, are also employed to generate theoretical spectra in ε. Critical point energies (CPs) from 0.91 to 1.49 eV are interpreted as energy separation between eg and t2g orbitals. CPs from 3.31 to 3.53 eV and 3.75 to 5.23 are interpreted as Mn d exchange splitting and strong charge transfer transitions, respectively. Direct and indirect bandgaps from Tauc-plots are identified in the range of 0.100–0.594 eV. Anisotropy presents in LaMnO3 on LaAlO3 is attributed to substantial distortion in the out-of-plane epitaxial strain compared to LaMnO3 on SrTiO3. These findings provide a comprehensive understanding of the origins and characteristics of features observed in optical properties of epitaxial LaMnO3, offering insights for development of optical and electronic applications based on these materials.

Theoretical Study of the Phonon and Electrical Conductivity Properties of Pure and Sr-Doped LaMnO3 Thin Films.

The film thickness, temperature, substrate and doping dependence of the phonon energy ω and damping γ, as well as the electrical conductivity, of pure and Sr-doped LaMnO3 thin films near the phase transition temperature TN are investigated using a microscopic model and the Green's function technique. Due to the strong spin-phonon interaction, there appears a kink at TN in the temperature dependence of ω(T) and γ(T). The softening and hardening of the ω = 495 cm-1 (A1g) and ω = 614 cm-1 (B2g) modes is explained by the different sign of the anharmonic spin-phonon interaction constant R. The damping increases with T for both cases because it is proportional to R2. ω decreases whereas γ increases with an increasing Sr concentration. This is due to the strain caused by the difference between the ionic radii of the La and Sr ions. The film thickness dependence is also considered. ω and γ increase strongly with the decreasing film thickness. The electrical conductivity is enhanced after the doping of the LMO thin films with Sr, which could be used for energy storage applications. The observed results are in good qualitative agreement with the experimental data.

Magneto-Conductive and Magnetic Properties in La<sub>1-<i>x</i></sub>Sr<i><sub>x</sub></i>MnO<sub>3 </sub>Thin Films on a-SiO<sub>2</sub> Substrates Produced by Metal Organic Decomposition Method

We have studied magneto-conductive and magnetic properties of La1-xSrxMnO3 (LSMO) thin films on a-SiO2 substrates produced by the metal organic decomposition (MOD) method. LSMO thin films for x = 0, 0.15 and 0.3 have been produced in a pure O2 gas atmosphere. Although LaMnO3 (LMO) single crystal is an antiferromagnetic insulator (AFI), LMO thin films we have produced show ferromagnetic metal (FM) properties for suitable heat treatment conditions. We consider that the excess of O2- ions in LMO thin films produced in a pure O2 gas atmosphere induces the strong hole self-doping into those and the LMO thin films change from AFI to FM. Whereas, the ordinary hole doping is also occurred in LSMO thin films at x > 0. Thus, the carrier doping for LSMO thin films at x > 0 is caused by the hole self-doping by O2- ions and the ordinary hole doping by the replacement of La3+ ions by Sr2+ ones. To investigate the crystallographic and surface structures of the LSMO thin films, X-ray diffraction and SEM measurements have been performed, respectively. From the X-ray diffraction measurement, we have found that all LSMO thin films have perovskite structure and are polycrystalline. From the SEM measurement, we have seen that the LSMO thin films are formed of the aggregation of LSMO fine particles. Electrical resistivities (ERs) and magneto-resistivity (MR) ratios of the LSMO thin films have been measured on the temperature dependence (4K-300K). From MR ratio measurements, the coercive forces of them have been obtained as a function of temperature, and the Curie temperatures have been estimated from the temperature dependences of the coercive forces. We have discussed the origin of the magneto-conductive and magnetic properties of LSMO thin films.

Effects of phase transition driven by cation vacancies on magnetism and electricity in LaxMnO3 thin films

The attractive physical properties of perovskite manganese make them fundamental building blocks for oxide spintronic devices. However, defects and lattice distortions can lead to extrinsic properties, especially cation vacancies, severely compromising device performance. In particularly, many intriguing properties, such as the emergence of magnetism and two-dimensional high-mobility electron gases, are closely related to cation vacancies. In this study, we deposited a series of LaxMnO3 epitaxial thin films with varying contents of La3+ vacancies on SrTiO3 (100) substrates, with the presence of La3+ vacancies verified by using X-ray diffraction, X-ray photoemission spectroscopy, X-ray absorption spectroscopy, and energy dispersive spectroscopy spectrum. The reduction in La3+ vacancies led to stronger ferromagnetism with an easy axis oriented along the (110) direction in LaMnO3 thin films, along with the appearance of a monoclinic phase, indicating that the ferromagnetism possibly originated from the three-dimensional d3z2−r2/dx2−y2-alternated orbital order rather than the Mn3+/Mn4+ double exchange effect. This result implies that the consistent regulation of cation vacancies by pulsed laser deposition can modulate both the structure and physical properties of manganate films, thereby enabling control over device properties.

Epitaxial strain manipulation of the cluster glass state in LaMnO3 films.

As a new-type magnetic state, the cluster glass state in manganite is arousing considerable attention due to its important theoretical value and extensive application prospects in condensed matter physics and spintronics. Due to the complex magnetic interactions, the cluster glass state is difficult to form and regulate in single films. Studies report a new phenomenon that epitaxial strain can regulate the formation of the cluster glass state in LaMnO3 (LMO) films. Comparing LMO thin films with different thicknesses grown on a (001)-oriented LaAlO3 (LAO) single crystal substrate, we found that the 20-nm-thick LMO film is more likely to form the cluster glass state than the 60-nm-thick and 120-nm-thick films. This can be attributed to the uneven distribution of strain and Mn ions in the depth profile. Our work demonstrates that thickness is an important method for regulating the formation of the cluster glass state in LMO films.

Crystallographic dependence of the electrical transport mechanism in La-Mn-O thermosensitive thin films

Bimetallic oxide materials with amorphous state usually exhibit singular peculiarities due to their periodic disorder structure, implying great potential applications as high-performance electronic devices. In this report, La-Mn-O thin films with different crystallographic features (amorphous and polycrystalline) were deposited on Si (100) substrates using magnetron sputtering method. The as-deposited thin films were successfully convert from the amorphous state to the polycrystalline state by tuning the post-annealing temperatures. X-ray diffraction (XRD) confirmed that La-Mn-O was amorphous at annealing temperatures of 500 °C, while the films were polycrystalline at higher annealing temperatures (600 °C and 700 °C). Scanning electron microscopy (SEM) and high-magnification transmission electron microscopy (HRTEM) distinguished the microscopic features of LaMnO3 thin films in polycrystalline and amorphous states. The effects of annealing temperatures and structural disorder on the temperature-dependent electrical transport properties of La-Mn-O thin films are investigated. The resistance-temperature relationship curves of both polycrystalline and amorphous films show negative temperature coefficient behavior, and the amorphous films follow more than one conduction mechanism. Results show that the electrical transport of the crystalline La-Mn-O films is mainly controlled by thermal activation mechanism, while the electron transport behavior of the amorphous film is simultaneously influenced by thermal activation and Mott VRH variable range hopping conduction.

The Progress on Magnetic Material Thin Films Prepared Using Polymer-Assisted Deposition.

Polymer-assisted deposition (PAD) has been widely used in the preparation of high-quality oxides and sulfides for basic research and applications. Specifically, diverse PAD-prepared magnetic material thin films such as ZnO, Ga2O3, SrRuO3, LaCoO3, LaMnO3, Y3Fe5O12, MoS2, MoSe2, and ReS2 thin films have been grown, in which thickness-dependent, strain-modulated, doping-mediated, and/or morphology-dependent room-temperature ferromagnetism (RTFM) have been explored. Inspired by the discovery of intrinsic low-temperature FM in two-dimensional (2D) systems prepared using mechanical exfoliation, the search for more convenient methods to prepare 2D ferromagnetic materials with high-temperature FM has seen explosive growth, but with little success. Fortunately, the very recent synthesis of 2D NiO by PAD has shed light on this challenge. Based on these abovementioned developments, the difficulties of PAD when preparing a-few-nanometer single-crystalline materials and the opportunities in PAD for novel materials such as chiral magnetic soliton material Cr1/3NbS2 are discussed.

Magnetic Proximity Effect in LaMnO3-LaFeO3 Bilayer

Here, we report the magnetic properties of LaMnO3, LaFeO3 thin films and their heterostructures, fabricated using Pulse laser deposition technique (PLD) on SrTiO3(001) substrate. The crystal structure, surface morphology signifies the phase pure epitaxial growth of LaMnO3 and LaFeO3 films and their heterostructure. The magnetic characteristics of individual LaMnO3 and LaFeO3 films along with their heterostructures were studied to explore the proximity effect of the different antiferromagnets. We demonstrate that LaMnO3 thin film shows ferromagnetic signal with inconspicuous Tc. The ferromagnetic signal is stronger in case of LaMnO3 grown on buffered LaFeO3 and LaFeO3 on top of LaMnO3. The change of Tc is analyzed in heterostructures as compared to the bare LaMnO3. Additionally, our study illustrates the variation of anisotropic energy and spin flop coupling between the interface with alternate growth sequence of heterojunctions.

Improving the sensitivity of LaMnO3 NTC films by Al ion implantation

The Al ion implantation was employed to modify the NTC characteristics of LaMnO3 thin films sputtered on Si/SiO2 substrates under different annealing temperatures. The crystal structure, morphology and ion distribution of the as-sputtered LaMnO3 thin films and as-annealed Al-implanted films were carefully evaluated. Results indicated that (LaMnAlxO3)y(Al2O3)1-y composite phase existed over the annealing temperature range after Al3+ implanting into the LaMnO3 film of perovskite phase. The film was nucleated throughout and the size of the grain decreased with the increase in annealing temperature. The Al3+ implantation promoted the reduction of oxygen vacancy concentration while leading to the reduction in the equilibrium oxygen vacancy. As a result, the Mn3+/Mn4+ ratio declined and the number of carriers reduced, which helped to increase the carrier migration barrier and activation energy. The direct manifestation of the latter is the increase of the thermal constant B value from 3192 K to 2111 K based on the premise of resistivity is closed. The successful modification of a traditional perovskite-type NTC material will bring an innovative perspective to the design of advanced functional film materials and provide ideas for further exploration of the material in high B and low resistivity temperature sensor applications.

Ionic liquid modulation of exchange bias in epitaxial LaMnO3 thin films

The magnetic ground state of LaMnO3 (LMO) thin film is still a controversial issue, even though various mechanisms, such as cation/anion non-stoichiometry, epitaxial strain, interfacial charge reconstruction, and orbital ordering, have been proposed. Here, exchange bias (EB) was introduced into a high-quality epitaxial LMO thin film via relatively low oxygen growth pressure. The EB in LMO was modulated by +2 V gating via ionic liquid method with increased EB field (HEB), coercivity (HC), blocking temperature (TB), and reduced ferromagnetic (FM) magnetization. However, the −2 V gating has a much weaker tunability. By investigating the change of structure, surface morphology, and Mn oxidation state in LMO thin films, the modulation of magnetic properties is attributed to the creation/annihilation of oxygen vacancy in an LMO thin film. The suppressed FM phase in LMO can be ascribed to reduced Mn valence, structure disorders, and structure transition. However, the enriched antiferromagnetic phase results from the transition of the pseudocubic structure to the distorted orthorhombic structure. This work not only highlights the importance of functional defects in perovskite oxides but also sheds light on the potential of electric-field modulation of magnetism in spintronic devices.

Epitaxial growth of LaMnO3 thin films on different single crystal substrates by polymer assisted deposition

Structure of epitaxial LaMnO3 thin films grown on different single crystal substrates by unconventional polymer assisted deposition (PAD) method was investigated. Epitaxial films were prepared from lanthanum manganite water based solutions deposited by spin coating on single crystal MgO (001), SrTiO3 (001) and SrTiO3 (110) substrates, and the influence of substrate type on the film structure was analysed. Better uniformity of the epitaxial LaMnO3 films on SrTiO3 substrates was obtained, but a non-stoichiometric La1-xMnO3 phase was formed after the heat treatment at 750 °C. In addition, the prepared thin films were multiple annealed at different temperatures up to 900 °C, in order to investigate importance of post-annealing treatment. Epitaxial nature of the prepared films was preserved after annealing at up to 900 °C and the structure rearrangement through formation of cell closer to bulk stochiometric LaMnO3 phase was observed.

One-Stage Hydrothermal Growth and Characterization of Epitaxial LaMnO3 Films on SrTiO3 Substrate.

Epitaxial LaMnO3 thin films were grown on SrTiO3 substrate using a one-stage hydrothermal route from La(NO3)3, MnCl2 and KMnO4 in an aqueous solution of 10 M KOH at 340 °C. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) indicate full coverage of LaMnO3 on the substrate. X-ray diffraction in the symmetric ω/2θ mode suggests the film has an out-of-plane preferred orientation along the [001] direction of the substrate. The LaMnO3 epitaxial thin film growth mechanism is proposed based on the analysis of the atomic sharp interface formed between LaMnO3 and the SrTiO3 substrate, as seen by aberration−corrected scanning transmission electron microscopy (AC−STEM) imaging in combination with electronic energy loss spectroscopy (EELS). Compared with the conventional vapor deposition methods, the one-stage hydrothermal route opens up a new way to fabricate complex oxide epitaxial heterostructures.

Observing structural distortions in complex oxides by x-ray photoelectron diffraction

The observation of structural distortions in complex oxides is becoming more important in order to explain their macroscopic behavior. X-ray photoelectron diffraction is an excellent technique to study the crystal structure and potentially observe oxygen distortions in an element-specific fashion. Its surface-sensitive character opens up the possibility to perform experiments on ultra-thin films without probing the substrate underneath. For BaBiO3 thin films, for example recent experimental results point towards a suppression of an oxygen breathing mode with decreasing film thickness resulting in a decreased energy band gap. As another example, a nontrivial electronic band structure is predicted for [111]-bilayers of LaMnO3. However, the likely presence of a Jahn–Teller distortion would suppress the topological phase. Here, the working principle of x-ray photoelectron diffraction is described and the data analysis required afterwards is discussed. X-ray photoelectron diffraction interference patterns are obtained for various thicknesses of BaBiO3 and LaMnO3 thin films. Experimental results are compared with multiple-scattering simulations. Although, indications for the structural distortions are observed, we discuss limitations of the technique in quantifying the displacement of the oxygen atoms.

Raman spectroscopy of the Jahn–Teller phonons in a magnetic LaMnO3 thin film grown on KTaO3

Bulk LaMnO3 is an A-type antiferromagnetic material in which the Jahn–Teller (JT) planes each have a ferromagnetic arrangement, but are stacked in antiparallel. Here, we report the growth of epitaxial LaMnO3 films on (001)-oriented cubic KTaO3 substrates in such a way that the JT plane is parallel to the nonmagnetic substrate. We verify the presence of the JT distortion and confirm the orientation of the plane by symmetry analysis with angle-resolved polarized Raman spectroscopy. The temperature evolution of the Raman spectra indicates that the B1g JT phonon softens below the magnetic transition temperature of ∼145 K, where ferro- or ferri-magnetism with magnetic easy axis along the out-of-plane direction is exhibited.

Dry reforming of methane over Ni supported on LaMnO3 thin films

Thin films of LaMnO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and studied as supports for Ni in the Dry Reforming of Methane (DRM). Scanning Transmission Electron Microscopy (STEM) with Energy-Dispersive X-ray Spectroscopy (EDS) demonstrated that LaMnO3 covered the support uniformly, and X-ray diffraction (XRD) showed that the LaMnO3 films maintained their perovskite structure after 5 redox cycles at 1073 K. The Ni also remained well dispersed after 5 redox cycles at 1073 K. The LaMnO3-supported catalyst was more active than Ni on the unmodified MgAl2O4 and showed superior resistance against coke formation. Finally, the results for Ni on the LaMnO3 films are compared to previous results for Ni on LaFeO3, CaTiO3, SrTiO3, and BaTiO3 films.

Raman imaging of ferroelastically configurable Jahn\u2013Teller domains in LaMnO3

The Jahn–Teller (JT) effect, through geometric deformation of molecules or local ionic lattices, lowers the overall energy of the system by removing electron degeneracy from partially occupied orbitals. Crystal symmetry lowered by JT distortion inevitably creates multiple variants of elastic and orbital-anisotropic states. Visualization and control of the domain/wall textures create a cornerstone to understand various correlated phenomena and explore wall properties. Here, we report the real-space observation of JT phonon and orbiton-related domains in a LaMnO3 thin film using confocal Raman spectromicroscopy. The characteristic symmetries of the JT-originated Raman modes allow us to detect and visualize the local population and orientation of the JT planes. Combined with a crystal structural analysis, we find that the formation of ferroelastic domains with W or W’ walls provides the basic framework for understanding JT domain textures. Furthermore, we demonstrate the JT domains can be manipulated by applying local external stress. Our findings provide a useful pathway for mechanically-tunable orbitronic applications.

Emergent Magnetic Phenomenon with Unconventional Structure in Epitaxial Manganate Thin Films.

A variety of emergent phenomena are enabled by interface engineering in the complex oxides heterostructures. While extensive attention is attracted to LaMnO3 (LMO) thin films for observing the control of functionalities at its interface with substrate, the nature of the magnetic phases in the thin film is, however, controversial. Here, it is reported that the ferromagnetism in two and five unit cells thick LMO films epitaxially deposited on (001)‐SrTiO3 substrates, a ferromagnetic/ferromagnetic coupling in eight and ten unit cells ones, and a striking ferromagnetic/antiferromagnetic pinning effect with apparent positive exchange bias in 15 and 20 unit cells ones are observed. This novel phenomenon in both 15 and 20 unit cells films indicates a coexistence of three magnetic orderings in a single LMO film. The high‐resolution scanning transmission electron microscopy suggests a P21/n to Pbnm symmetry transition from interface to surface, with the spatial stratification of MnO6 octahedral morphology, corresponding to different magnetic orderings. These results can shed some new lights on manipulating the functionality of oxides by interface engineering.

Effect of substrate orientation on formation of cluster glass state in epitaxial LaMnO3 thin films

Cluster glass state, which is closely related to some special physical phenomena, has attracted extensive attention. Herein, we report a new phenomenon that is the substrate orientation can influence the formation of the cluster glass state in LaMnO3 (LMO) films. To explore the effect of substrate orientation on the formation of cluster glass state, the LMO thin films are epitaxially grown on (001)-, (110)- and (111)-oriented LaAlO3 (LAO) single crystal substrates by pulsed laser deposition (PLD), and the cluster glass state in which is investigated. The results show that the substrate orientation has a great influence on the formation of cluster glass state in the LMO epitaxial films. The LMO thin film grown on (001)-oriented LAO substrates is more likely to form cluster glass state than those grown on (110)- and (111)-oriented LAO substrates. This can be attributed to the different degrees of the ferromagnetic and antiferromagnetic interactions, which is caused by the different crystalline orientations and strain states of the epitaxial LMO thin films.

Electret formation in transition metal oxides by electrochemical amorphization

Transition metal oxides (TMOs) are an important class of materials that show a wide range of functionalities involving spin, charge, and lattice degrees of freedom. The strong correlation between electrons in d-orbitals and the multivalence nature give rise to a variety of exotic electronic states ranging from insulator to superconductor and cause intriguing phase competition phenomena. Despite a burst of research on the multifarious functionalities in TMOs, little attention has been paid to the formation and integration of an electret—a type of quasi-permanent electric field generator useful for nanoscale functional devices as an electric counterpart to permanent magnets. Here, we find that an electret can be created in LaMnO3 thin films by tip-induced electric fields, with a considerable surface height change, via solid-state electrochemical amorphization. The surface charge density of the formed electret area reaches ~400 nC cm−2 and persists without significant charge reduction for more than a year. The temporal evolution of the surface height, charge density, and electric potential are systematically examined by scanning probe microscopy. The underlying mechanism is theoretically analyzed based on a drift-diffusion-reaction model, suggesting that positively charged particles, which are likely protons produced by the dissociation of water, play crucial roles as trapped charges and a catalysis to trigger amorphization. Our finding opens a new horizon for multifunctional TMOs.