Search Results (40)

Various types of strain, as well as chemical pressure induced by dopants, can effectively tailor the performance of perovskite thin films, including their optical, electrical or photoelectrochemical properties. The control of these functional properties through such engineering techniques is key to fulfilling the application-specific requirements of ferroelectric devices in various fields. Numerous models and experimental data have been published on this subject, especially on ferrite-based ferroelectric materials. Within this paper, the mechanisms of tuning ferroelectric intrinsic properties, such as polarization and ferroelectric domain configurations, through epitaxial strain and doping, as well as the role of these techniques in influencing functional properties such as dielectric and photoelectrochemical ones, are presented. This review examines the significant improvements in dielectric properties and photoelectrochemical efficiency achieved by the strategical control of key functionalities including dielectric losses, domain structures, charge separation and surface reactions in strained/doped ferroelectric thin films, highlighting the advancements and research progress made in this field in recent years. Full article

Hole-doped manganese oxides exhibit a gigantic negative magnetoresistance, referred to as colossal magnetoresistance (CMR), owing to the interplay between double-exchange (DE) ferromagnetic metal and charge-ordered antiferromagnetic insulator/semiconductor phases. Magnetoresistive manganites display a sharp resistivity drop at the metal–insulator transition temperature (T^MI). CMR effects in perovskite manganites, specifically La_0.67Ca_0.33MnO₃ (La-Ca-Mn-O or LCMO), have been extensively investigated. This review paper provides a comprehensive introduction to the crystallographic structure, as well as the electronic and magnetic properties, of LCMO films. Furthermore, we delve into a detailed discussion of the effects of epitaxial strain induced by different substrates on LCMO films. Additionally, we review the early findings and diverse applications of LCMO thin films. Finally, we outline potential challenges and prospects for achieving superior LCMO film properties. Full article

Strontium aluminate, with suitable lattice parameters and environmentally friendly water solubility, has been strongly sought for use as a sacrificial layer in the preparation of freestanding perovskite oxide thin films in recent years. However, due to this material’s inherent water solubility, the methods used for the preparation of epitaxial films have mainly been limited to high-vacuum techniques, which greatly limits these films’ development. In this study, we prepared freestanding single-crystal perovskite oxide thin films on strontium aluminate using a simple, easy-to-develop, and low-cost chemical full-solution deposition technique. We demonstrate that a reasonable choice of solvent molecules can effectively reduce the damage to the strontium aluminate layer, allowing successful epitaxy of perovskite oxide thin films, such as 2-methoxyethanol and acetic acid. Molecular dynamics simulations further demonstrated that this is because of their stronger adsorption capacity on the strontium aluminate surface, which enables them to form an effective protective layer to inhibit the hydration reaction of strontium aluminate. Moreover, the freestanding film can still maintain stable ferroelectricity after release from the substrate, which provides an idea for the development of single-crystal perovskite oxide films and creates an opportunity for their development in the field of flexible electronic devices. Full article

In this study, a detailed structural characterization of epitaxial ${\text{La}}_{0.6}$${\text{Sr}}_{0.4}$${\text{CoO}}_{3-\delta }$ (LSC) films grown in (100), (110), and (111) orientations was conducted. LSC is a model air electrode material in solid oxide fuel and electrolysis cells and understanding the correlation of bulk structure and catalytic activity is essential for the design of future electrode materials. Thin films were grown on single crystals of the perovskite material ${\text{La}}_{0.95}$${\text{Sr}}_{0.05}$${\text{Ga}}_{0.95}$${\text{Mg}}_{0.05}$${\text{O}}_{3-\delta }$ cut in three different directions. This enabled an examination of structural details at the atomic scale for a realistic material combination in solid oxide cells. The investigation involved the application of atomic force microscopy, X-ray diffraction, and high-resolution transmission electron microscopy to explore the distinct properties of these thin films. Interestingly, ordering phenomena in both cationic as well as anionic sublattices were found, despite the fact that the thin films were never at higher temperatures than 600 °C. Cationic ordering was found in spherical precipitates, whereas the ordering of oxygen vacancies led to the partial transition to brownmillerite in all three orientations. Our results indicate a very high oxygen vacancy concentration in all three thin films. Lattice strains in-plane and out-of-plane was measured, and its implications for the structural modifications are discussed. Full article

The growth of epitaxial thin films from the Ruddlesden–Popper series of strontium iridates by magnetron sputtering is analyzed. It was found that, even using a non-stoichiometric target, the films formed under various conditions were consistently of the perovskite-like n = ∞ SrIrO₃ phase, with no evidence of other RP series phases. A detailed inspection of the temperature–oxygen phase diagram underscored that kinetics mechanisms prevail over thermodynamics considerations. The analysis of the angular distribution of sputtered iridium and strontium species indicated clearly different spatial distribution patterns. Additionally, significant backsputtering was detected at elevated temperatures. Thus, it is assumed that the interplay between these two kinetic phenomena is at the origin of the preferential nucleation of the SrIrO₃ phase. In addition, strategies for controlling cation stoichiometry off-axis have also been explored. Finally, the long-term stability of the films has been demonstrated. Full article

Pyroelectric materials, are those materials with the property that in the absence of any externally applied electric field, develop a built-in spontaneous polarization in their unit cell structure. They are regarded as ideal detector elements for infrared applications because they can provide fast response time and uniform sensitivity at room temperature over all wavelengths. Crystals of the perovskite Lead Titanate (PbTi${\mathrm{O}}_3$) family show pyroelectric characteristics and undergo structural phase transitions. They have a high Curie temperature (the temperature at which the material changes from the ferroelectric (polar) to the paraelectric (nonpolar) phase), high pyroelectric coefficient, high spontaneous polarization, low dielectric constant, and constitute important component materials not only useful for infrared detection, but also with vast applications in electronic, optic, and Micro-electromechanical systems (MEMS) devices. However, the preparation of large perfect, and pure single crystals of PbTi${\mathrm{O}}_3$ is challenging. Additionally, difficulties arise in the application of such bulk crystals in terms of connection to processing circuits, large size, and high voltages required for their operation. A number of thin film fabrication techniques have been proposed to overcome these inadequacies, among which, magnetron sputtering has demonstrated many potentials. By addressing these aspects, the review article aims to contribute to the understanding of the challenges in the field of pyroelectric materials, highlight potential solutions, and showcase the advancements and potentials of pyroelectric perovskite series including PbZrTiO₃ (PZT), ${\mathrm{P}\mathrm{b}}_{\mathrm{x}}{\mathrm{C}\mathrm{a}}_{1-\mathrm{x}}$ (PZN-PT), etc. for which PbTi${\mathrm{O}}_3$ is the end member. The review is presented in two parts. Part 1 focuses on material aspects, including preparation methods using magnetron sputtering and material characterization. We take a tutorial approach to discuss the progress made in epitaxial growth of lead titanate-based ceramics prepared by magnetron sputtering and examine how processing conditions may affect the crystalline quality of the growing film by linking to the properties of the substrate/buffer layer, growth substrate temperature, and the oxygen partial pressure in the gas mixture. Careful control and optimization of these parameters are crucial for achieving high-quality thin films with desired structural and morphological characteristics. Full article

The strain engineering effects induced by different means, e.g., the substrate lattice mismatch and/or chemical doping, on the functional properties of perovskite thin films have triggered interest in the use of these materials in different applications such as energy storage/generation or photonics. The effects of the film’s thickness and strain state of the structure for the lead-free perovskite ferrite-based materials (BiFeO₃-BFO; Y-doped BiFeO₃-BYFO; LaFeO₃-LFO) on their functional properties are highlighted here. As was previously demonstrated, the dielectric properties of BFO epitaxial thin films are strongly affected by the film thickness and by the epitaxial strain induced by the lattice mismatch between substrate and film. Doping the BiFeO₃ ferroelectric perovskite with rare-earth elements or inducing a high level of structural deformation into the crystalline structure of LaFeO₃ thin films have allowed the tuning of functional properties of these materials, such as dielectric, optical or photocatalytic ones. These changes are presented in relation to the appearance of complex ensembles of nanoscale phase/nanodomains within the epitaxial films due to strain engineering. However, it is a challenge to maintain the same level of epitaxial strain present in ultrathin films (<10 nm) and to preserve or tune the positive effects in films of thicknesses usually higher than 30 nm. Full article

Tellurium oxides of the ATeO₃ form typically do not crystallize in perovskite structures. Here, we show that perovskite-like ATeO₃ (A = Ca, Sr, Ba) thin films can be grown on perovskite single-crystal substrates via epitaxial stabilization. These films are stable with high optical bandgaps, low dielectric losses, and a high electric breakdown strength. Hysteretic dielectric behavior found in SrTeO₃ and BaTeO₃ strongly suggests the presence of antiferroelectricity and ferroelectricity, respectively. These properties make perovskite tellurium oxides possibly appealing candidates for thin film coating or insulator materials in advanced microelectronics. Tellurium oxides constitute a largely unexplored class of materials that might show new and interesting functionalities in epitaxial thin-films. Our work encourages new work within this field. Full article

In this work, three sets of single crystalline films (SCF) of Al₂O₃:Mn sapphire, YAlO₃:Mn perovskite (YAP:Mn), and Y₃Al₅O₁₂:Mn garnet (YAG:Mn), with a nominal Mn content of 0.1%, 1%, and 10 atomic percent (at.%) in the melt-solutions, were crystallized by the liquid phase epitaxy (LPE) method onto sapphire, YAP and YAG substrates, respectively. We have also calculated the average segregation coefficient of Mn ions for Al₂O₃:Mn, YAP:Mn and YAG:Mn SCFs with Mn content in the melt-solution in the 0.1–10% concentration range, which was equal to 0.1, 0.14 and 0.2, respectively. The main goal of the conducted research was the spectroscopic determination of the preferable valence states of manganese ions which were realized in the SCFs of sapphire, perovskite and garnet depending on the Mn content. For this purpose, the absorption, cathodoluminescence (CL), photoluminescence (PL) emission/excitation spectra and PL decay kinetics of Al₂O₃:Mn, YAP:Mn and YAG:Mn SCFs with different Mn concentrations were studied. Based on the CL and PL spectra, we showed that Mn ions, depending on the Mn content in the melt-solution, are incorporated in Al₂O₃:Mn, YAP:Mn and YAG:Mn SCFs in the different charged states and are located in the different crystallographic positions of the mentioned oxide lattices. We have observed the presence of the luminescence of Mn⁴⁺, Mn³⁺ and Mn²⁺ valence states of manganese ions in CL spectra in all SCFs under study with 0.1 and 1% Mn concentrations. Namely, the Mn⁴⁺ ion valence state with the main sharp emission bands peaked at 642 and 672 nm, related to the ²E → ⁴A₂ transitions, was found in the luminescence spectra of the all studied Al₂O₃:Mn SCFs. The luminescence of the Mn²⁺ valence state was found only in YAP:Mn and YAG:Mn SCFs, grown from melt solution with 1% Mn content, in the emission bands peaked at 525 and 560 nm, respectively, related to the ⁴T₁ → ⁶A₁ transitions. The PL and CL spectra of YAP:Mn and YAG:Mn SCFs with the Mn content in the 0.1–1% range show that the main valence state of manganese ions in these films is Mn³⁺ with the main emission bands peaking at 655 and 608 nm, respectively, related to the ¹T₂ → ⁵E transitions. Meanwhile, higher than 1% Mn content in the melt solution causes a strong concentration quenching of luminescence of all Mn centers in Al₂O₃:Mn, YAP:Mn and YAG:Mn SCFs. Full article

Substrate-induced strains can significantly influence the structural properties of epitaxial thin films. In ferroelectrics, this might lead to significant changes in the functional properties due to the strong electromechanical coupling in those materials. To study this in more detail, epitaxial Ba${}_{0.7}$Sr${}_{0.3}$TiO${}_3$ films, which have a perovskite structure and a structural phase transition close to room temperature, were grown with different thicknesses on REScO${}_3$ (RE–rare earth element) substrates having a smaller lattice mismatch compared to SrTiO${}_3$. A fully strained SrRuO${}_3$ bottom electrode and Pt top contacts were used to achieve a capacitor-like architecture. Different X-ray diffraction techniques were applied to study the microstructure of the films. Epitaxial films with a higher crystalline quality were obtained on scandates in comparison to SrTiO${}_3$, whereas the strain state of the functional layer was strongly dependent on the chosen substrate and the thickness. Differences in permittivity and a non-linear polarization behavior were observed at higher temperatures, suggesting that ferroelectricity is supressed under tensile strain conditions in contrast to compressive strain for our measurement configuration, while a similar reentrant relaxor-like behavior was found in all studied layers below 0$°\mathrm{C}$. Full article

Accurate structure analysis of epitaxial perovskite thin films is a fundamental step towards the ability to tune their physical properties as desired. Precession-assisted electron diffraction tomography (PEDT) has proven to be an effective technique for performing ab initio structure solutions and refinements for this class of materials. As the film thickness or the region of interest (ROI) decrease in size, the capacity to collect PEDT data with smaller electron beams is a key parameter and ROI tracking becomes a major issue. To circumvent this problem, we considered here an alternative approach to acquiring data by combining PEDT with a scan over an area, extracting the intensities collected at different positions and using them to perform accurate structure refinements. As a proof of concept, a Scanning Precession Electron Tomography (SPET) experiment is performed on a 35 nm thick perovskite $PrV{O}_3$(PVO) film deposited on a $SrTi{O}_3$ (STO) substrate. This way, it was possible to detect small changes in the PVO structure along the film thickness, from the variation in unit cell parameters to atomic positions. We believe that SPET has the potential to become the standard procedure for the accurate structure analysis of ROIs as small as 10 nm. Full article

Lead zirconate titanate (PZT) films have shown great potential in piezoelectric micro-electronic-mechanical system (piezo-MEMS) owing to their strong piezoelectric response. However, the fabrication of PZT films on wafer-level suffers with achieving excellent uniformity and properties. Here, we successfully prepared perovskite PZT films with similar epitaxial multilayered structure and crystallographic orientation on 3-inch silicon wafers, by introducing a rapid thermal annealing (RTA) process. Compared to films without RTA treatment, these films exhibit (001) crystallographic orientation at certain composition that expecting morphotropic phase boundary. Furthermore, dielectric, ferroelectric and piezoelectric properties on different positions only fluctuate within 5%. The relatively dielectric constant, loss, remnant polarization and transverse piezoelectric coefficient are 850, 0.1, 38 μC/cm² and −10 C/m², respectively. Both uniformity and properties have reached the requirement for the design and fabrication of piezo-MEMS devices. This broadens the design and fabrication criteria for piezo-MEMS, particularly for piezoelectric micromachined ultrasonic transducers. Full article

Rare earth nickel-based perovskite oxides (RENiO₃) have been widely studied over recent decades because of their unique properties. In the synthesis of RENiO₃ thin films, a lattice mismatch frequently exists between the substrates and the thin films, which may affect the optical properties of RENiO₃. In this paper, the first-principles calculations were employed to study the electronic and optical properties of RENiO₃ under strain. The results showed that with the increase in tensile strength, the band gap generally shows a widening trend. For optical properties, the absorption coefficients increase with the enhancement of photon energies in the far-infrared range. The compressive strain increases the light absorption, while the tensile strain suppresses it. For the reflectivity spectrum in the far-infrared range, a minimum reflectivity displays around the photon energy of 0.3 eV. The tensile strain enhances the reflectivity in the range of 0.05–0.3 eV, whereas it decreases it when the photon energies are larger than 0.3 eV. Furthermore, machine learning algorithms were applied and found that the planar epitaxial strain, electronegativity, volume of supercells, and rare earth element ion radius play key roles in the band gaps. Photon energy, electronegativity, band gap, the ionic radius of the rare earth element, and the tolerance factor are key parameters significantly influencing the optical properties. Full article

All-inorganic perovskites, with their low-cost, simple processes and superior heat stability, have become potential candidate materials for photodetectors (PDs). However, they have no representative responsivity in the deep-ultraviolet (UV) wavelength region. As a new-generation semiconductor, gallium oxide (Ga₂O₃), which has an ultrawide bandgap, is appropriate for solar-blind (200 nm–280 nm) deep-UV detection. In this work, ultrawide-bandgap Ga₂O₃ was introduced into an inorganic perovskite device with a structure of sapphire/β-Ga₂O₃/Indium Zinc Oxide (IZO)/CsPbBr₃. The performance of this perovskite PD was obviously enhanced in the deep UV region. A low-cost, vacuum-free Mist-CVD was used to realize the epitaxial growth of β-Ga₂O₃ film on sapphire. By introducing the Ga₂O₃ layer, the light current of this heterojunction PD was obviously enhanced from 10⁻⁸ to 10⁻⁷, which leds its detectivity (D*) to reach 1.04 × 10¹² Jones under a 254 nm light illumination with an intensity of 500 μW/cm² at a 5 V bias. Full article

In this work, we report a systematic study of the influence of film thickness on the structural and magnetic properties of epitaxial thin films of Pr_2−δNi_1−xMn_1+xO_6−y (PNMO) double perovskite grown on top of two different (001)-SrTiO₃ and (001)-LaAlO₃ substrates by RF magnetron sputtering. A strong dependence of the structural and magnetic properties on the film thickness is found. The ferromagnetic transition temperature (T_C) and saturation magnetization (Ms) are found to decrease when reducing the film thickness. In our case, the thinnest films show a loss of ferromagnetism at the film-substrate interface. In addition, the electronic structure of some characteristic PNMO samples is deeply analyzed using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) measurements and compared with theoretical simulations. Our results show that the oxidation states of Ni and Mn ions are stabilized as Ni²⁺ and Mn⁴⁺, thus the ferromagnetism is mainly due to Ni²⁺-O-Mn⁴⁺ superexchange interactions, even in samples with poor ferromagnetic properties. XMCD results also make evident large variations on the spin and orbital contributions to the magnetic moment as the film’s thickness decreases. Full article