Formation of self-organized Mn3O4 nanoinclusions in LaMnO3 films

et al.We present a single-step route to generate ordered nanocomposite thin films of secondary phase inclusions (Mn3O4) in a pristine perovskite matrix (LaMnO3) by taking advantage of the complex phase diagram of manganese oxides. We observed that in samples grown under vacuum growth conditions from a single LaMnO3 stoichiometric target by Pulsed Laser Deposition, the most favorable mechanism to accommodate Mn2+ cations is the spontaneous segregation of self-assembled wedge-like Mn3O4 ferrimagnetic inclusions inside a LaMnO3 matrix that still preserves its orthorhombic structure and its antiferromagnetic bulk-like behavior. A detailed analysis on the formation of the self-assembled nanocomposite films evidences that Mn3O4 inclusions exhibit an epitaxial relationship with the surrounding matrix that it may be explained in terms of a distorted cubic spinel with slight (~9°) c-axis tilting. Furthermore, a Ruddlesden-Popper La2MnO4 phase, helping to the stoichiometry balance, has been identified close to the interface with the substrate. We show that ferrimagnetic Mn3O4 columns influence the magnetic and transport properties of the nanocomposite by increasing its coercive field and by creating local areas with enhanced conductivity in the vicinity of the inclusions.Financial support from the Spanish Ministry of Economy and Competitiveness, through the “Severo Ochoa” Program for Centres of Excellence in R&D (SEV-2015-0496 and SEV 2013-0295), Projects MAT2011-29081 and MAT2015-71664-R and Ministry of Education and Science of Serbia (Grant—III45018) is acknowledged. This work has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No. 645658 (DAFNEOX Project). NB thanks the Spanish MINECO for financial support through the FPI program.Peer reviewedPeer Reviewe

Formation of Self-Organized Mn3O4 Nanoinclusions in LaMnO3 Films

We present a single-step route to generate ordered nanocomposite thin films of secondary phase inclusions (Mn3O4) in a pristine perovskite matrix (LaMnO3) by taking advantage of the complex phase diagram of manganese oxides. We observed that in samples grown under vacuum growth conditions from a single LaMnO3 stoichiometric target by Pulsed Laser Deposition, the most favorable mechanism to accommodate Mn2+ cations is the spontaneous segregation of self-assembled wedge-like Mn3O4 ferrimagnetic inclusions inside a LaMnO3 matrix that still preserves its orthorhombic structure and its antiferromagnetic bulk-like behavior. A detailed analysis on the formation of the self-assembled nanocomposite films evidences that Mn3O4 inclusions exhibit an epitaxial relationship with the surrounding matrix that it may be explained in terms of a distorted cubic spinel with slight (~9°) c-axis tilting. Furthermore, a Ruddlesden-Popper La2MnO4 phase, helping to the stoichiometry balance, has been identified close to the interface with the substrate. We show that ferrimagnetic Mn3O4 columns influence the magnetic and transport properties of the nanocomposite by increasing its coercive field and by creating local areas with enhanced conductivity in the vicinity of the inclusions

Field Effect and Magnetically Induced Capacitive Tuning in Hole Doped La1-xSRXMnO3

Electrostatic modulation of interface conduction between semiconductors and insulating oxides is the foundation of semiconductor technology. This field effect concept can be applied on complex oxides, such as high temperature superconductors and colossal magnetoresistive manganites, in order to create new electronic and magnetic phases. Competition and coexistence of multiple nanoscale phases make them exciting to study around phase transitions. This study on hole doped La1-xSrxMnO3 systems has a two-fold purpose. One is the demonstration of the field effect on La1-xSrxMnO3 (x = 0.125, 0.2, 0.3, 0.5) thin films. It is an important step towards electrostatic control of material properties; however, a challenging task because of their charge carrier densities of 0.01-1 hole/unit cell, a few orders of magnitude larger than in doped semiconductors. Control by linear dielectrics needs huge, constantly applied bias. Energy efficient tuning with low voltages requires highly polar ferroelectric. Pb(Zr0.2Ti0.8)O3 was chosen, whose remanence provides 0.5 charge carrier/unit cell on the manganite/ferroelectric interface. La1-xSrxMnO3/Pb(Zr0.2Ti0.8)O3 heterostructures were synthesized by pulsed laser epitaxy and remarkable conduction modifications were observed in the La1-xSrxMnO3. This can be a strong foundation of a new tool to research electronic oxides. The second purpose of this work is to utilize the phase separation in manganites. There has been extensive research on multiferroic materials, in which dielectric and magnetic responses are controlled by magnetic and electric field, respectively. In order to demonstrate magnetically tuned capacitance, insulating La7/8Sr1/8MnO3 was studied. Drastic capacitance change in magnetic field was shown through a phase transitions and explained in the framework of electronic phase separation. It makes this material eligible for high frequency magnetoelectric applications. Modulating charge carriers, mobility and magnetism in magnetic oxides, superconductors and superlattices has a great impact on the emerging field of oxide electronics. These compounds overcome the scaling limitations of conventional semiconductors; using low operation voltage oxide ferroelectrics lowers energy consumption. This thesis shows that changing fundamental physical properties of complex oxides on the atomic scale is possible by ferroelectric field effect. This technique is proposed as a tool to study thin films, artificially stacked structures and to induce and optimize novel phases and phenomena

Advances in materials design for all-solid-state batteries: From bulk to thin films

All-solid-state batteries (SSBs) are one of the most fascinating next-generation energy storage systems that can provide improved energy density and safety for a wide range of applications from portable electronics to electric vehicles. The development of SSBs was accelerated by the discovery of new materials and the design of nanostructures. In particular, advances in the growth of thin-film battery materials facilitated the development of all solid-state thin-filmbatteries (SSTFBs)-expanding their applications to microelectronics such as flexible devices and implantable medical devices. However, critical challenges still remain, such as low ionic conductivity of solid electrolytes, interfacial instability and difficulty in controlling thin-film growth. In this review, we discuss the evolution of electrode and electrolyte materials for lithium-based batteries and their adoption in SSBs and SSTFBs. We highlight novel design strategies of bulk and thin-film materials to solve the issues in lithium-based batteries. We also focus on the important advances in thin-film electrodes, electrolytes and interfacial layers with the aim of providing insight into the future design of batteries. Furthermore, various thin-film fabrication techniques are also covered in this review

Systematic Characterization and Analysis of Resistance from Conductors and Electrodes for Solid Oxide Fuel Cells

Solid oxide fuel cells are all ceramic devices that generate electricity by direct electrochemical reactions of a fuel and oxidizer. Recent efforts are underway to reduce the operating temperature of solid oxide fuel cells which allow these devices to become more economically competitive. However, at decreased temperatures the resistance from key electrochemical processes greatly increases. The presented work encompasses the characterization and analysis of resistances from conductors and electrodes in solid oxide fuel cells. Ionic conductivity is a thermally activated process; therefore, the conductivity of the ion conducting phase must be improved for suitable operation at lower temperatures. Ionic transport along and across grain boundaries differ distinctly between polycrystalline solids with convention and nanometers sized grains. Ionic conductivity is often greater in the grain boundaries than compared to the grain bulk due to an accumulation of charge carriers. The Van der Pauw technique was leveraged in this worked to measure the conductivity of thin films with thicknesses on the order of nanometers. The results showed that ionic conduction within nanostructured thin films exceeds that of conventional polycrystalline materials. Furthermore, there is a need to identify the resistance that arises from individual electrochemical processes. Electrochemical impedance spectroscopy (EIS) is a technique regularly employed to analyze the resistance from electrochemical processes in the electrodes. Distribution of relaxation times has been applied to the impedance spectrum obtained through EIS. This high resolution plot allowed for the identification of resistances from individual electrochemical impedance processes. The resistances from gas diffusion in the anode and cathode, electrical charge transfer, and transport of ions through the ionic phase have been identified through distribution of relaxation times

Preparation and properties of high dose nitrogen implanted epitaxially grown gadolinium oxide on silicon

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Study of Multiferroic Properties of Ferroelectric- Ferromagnetic Heterostructures BZT-BCT/LSMO

Currently, there has been a flurry of research focused on multiferroic materials due to their potential applications. Lead (Pb)-based ferroelectric and multiferroic materials (PZT, PMN-PT, PZN-PT etc.) have been widely used for sensors, actuators, and electro-mechanical applications due to their excellent dielectric and piezoelectric properties. However, these materials are facing global restriction due to the toxicity of Pb. In this thesis, multiferroic properties of ferroelectric-ferromagnetic heterostructures consist of Pb-free perovskite oxides 0.5Ba(Zr0.2Ti0.8)O3-0.5 (Ba0.7 Ca0.3)TiO3 (BZT-BCT) and La0.7Sr0.3MnO3 (LSMO) have been studied. The heterostructures BZT-BCT/LSMO were fabricated on LaAlO3 (LAO) and Pt substrates by pulsed laser deposition. Structural and crystalline qualities of the films have been investigated through theta-2theta scan, rocking curve, and phi-scan of X-Ray diffraction (XRD) and Raman spectroscopy. Ferroelectric and ferromagnetic properties have been characterized using the Sawyer-Tower method, a SQUID magnetometer, and Ferromagnetic resonance (FMR) spectroscopy. A well-behaved magnetization-magnetic field (M-H) hysteresis has been observed in LSMO as well as heterostructures, indicating ferromagnetism in the films. FMR spectroscopy data support the static magnetization data obtained using SQUID. These results may guide the development of next-generation lead-free ferroelectric-ferromagnetic heterostructures for magnetoelectric device applications

Advances in Materials Design for All-Solid-state Batteries: From Bulk to Thin Films

All-solid-state batteries (SSBs) are one of the most fascinating next-generation energy storage systems that can provide improved energy density and safety for a wide range of applications from portable electronics to electric vehicles. The development of SSBs was accelerated by the discovery of new materials and the design of nanostructures. In particular, advances in the growth of thin-film battery materials facilitated the development of all solid-state thin-film batteries (SSTFBs)—expanding their applications to microelectronics such as flexible devices and implantable medical devices. However, critical challenges still remain, such as low ionic conductivity of solid electrolytes, interfacial instability and difficulty in controlling thin-film growth. In this review, we discuss the evolution of electrode and electrolyte materials for lithium-based batteries and their adoption in SSBs and SSTFBs. We highlight novel design strategies of bulk and thin-film materials to solve the issues in lithium-based batteries. We also focus on the important advances in thin-film electrodes, electrolytes and interfacial layers with the aim of providing insight into the future design of batteries. Furthermore, various thin-film fabrication techniques are also covered in this review

Pyroelectric Materials for Uncooled Infrared Detectors: Processing, Properties, and Applications

Uncooled pyroelectric detectors find applications in diverse and wide areas such as industrial production; automotive; aerospace applications for satellite-borne ozone sensors assembled with an infrared spectrometer; health care; space exploration; imaging systems for ships, cars, and aircraft; and military and security surveillance systems. These detectors are the prime candidates for NASA s thermal infrared detector requirements. In this Technical Memorandum, the physical phenomena underlying the operation and advantages of pyroelectric infrared detectors is introduced. A list and applications of important ferroelectrics is given, which is a subclass of pyroelectrics. The basic concepts of processing of important pyroelectrics in various forms are described: single crystal growth, ceramic processing, polymer-composites preparation, and thin- and thick-film fabrications. The present status of materials and their characteristics and detectors figures-of-merit are presented in detail. In the end, the unique techniques demonstrated for improving/enhancing the performance of pyroelectric detectors are illustrated. Emphasis is placed on recent advances and emerging technologies such as thin-film array devices and novel single crystal sensors