Strain Controlled Functionalities in Lightly Doped Manganite Perovskite Epitaxial Thin Films Grown by Pulsed Laser Deposition

Strain Controlled Functionalities in Lightly Doped Manganite Perovskite Epitaxial Thin Films Grown by Pulsed Laser Deposition

Author: Richard Teboh Mbatang

Publisher:

Published: 2018

Total Pages: 188

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Functional Oxides have been widely studied in the last decades because of their fascinating properties as ferromagnetism, ferroelectricity, superconductivity and multiferroicity. The widely studied complex oxides are the perovskite and the hexagonal oxides. Intriguing phenomena have been observed in epitaxial thin films of manganite perovskites, which greatly differed from those of bulk material. Some of the interesting properties of lightly doped manganite oxide thin films, especially La0.9Sr0.1MnO3 thin films, are an enhanced magnetoresistance (MR) and temperature coefficient of resistance (TCR). The physical properties of these films are related to the effects that occur at the interface. Some of these interfacial effects includes defect formation, charge transfer, exchange coupling, strain, interfacial reconstruction and cation intermixing. The fast development of new characterization techniques have made the study of interfacial effects easy. Fabrication techniques such as Pulsed Laser Deposition (PLD) have been employed to produce interfaces with great atomic precision. Selecting materials with the right lattice mismatch and optimization of the growth conditions as laser repetition rate, temperature, oxygen pressure, substrate-target distance and laser energy are crucial in growth of epitaxial thin films for functional device application. In addition to these, selecting the right proposition of the various phase is important in achieving the right microstructure for composite films. The main focus of this dissertation is to investigate the relationship between structure and magneto-transport properties in lightly doped manganite perovskite thin films with the concentration on 10% strontium doped lathanum manganese oxide, La0.9Sr0.1MnO3 (LSMO) grown by Pulsed Laser Deposition (PLD). We grew films of different thicknesses (15 nm, 30 nm, 75 nm) and on different substrates ((001) LaAlO3 (LAO, (001) SrLaGaO4 (LSGO), (110), GdScO3 (DSO) and (110) GaScO3). We found that thinner films show highly enhanced magnetic and transport properties while thicker films exhibit low transport and magnetic properties due to strain relaxation. We also observed that compressive strain enhanced magnetic (saturation magnetization, Curie temperature (Tc)) and transport properties (metal-insulating transition (MIT), magnetoresistance (MR), temperature coefficient of resistance (TCR)). The enhancement of magnetic and transport properties were attributed to the suppression of Jahn-Teller distortion, electron-phonon coupling and the enhancement of double exchange coupling. In summary, strain can be used to tune the physical properties of expitaxial thin films for technological applications.


Surface Control of Epitaxial Manganite Films Via Oxygen Pressure

Surface Control of Epitaxial Manganite Films Via Oxygen Pressure

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Published: 2015

Total Pages: 12

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The trend to reduce device dimensions demands increasing attention to atomic-scale details of structure of thin films as well as to pathways to control it. We found that this is of special importance in the systems with multiple competing interactions. We have used in situ scanning tunneling microscopy to image surfaces of La5/8Ca3/8MnO3 films grown by pulsed laser deposition. The atomically resolved imaging was combined with in situ angle-resolved X-ray photoelectron spectroscopy. We find a strong effect of the background oxygen pressure during deposition on structural and chemical features of the film surface. Deposition at 50 mTorr of O2 leads to mixed-terminated film surfaces, with B-site (MnO2) termination being structurally imperfect at the atomic scale. Moreover, a relatively small reduction of the oxygen pressure to 20 mTorr results in a dramatic change of the surface structure leading to a nearly perfectly ordered B-site terminated surface with only a small fraction of A-site (La, Ca)O termination. This is accompanied, however, by surface roughening at a mesoscopic length scale. The results suggest that oxygen has a strong link to the adatom mobility during growth. The effect of the oxygen pressure on dopant surface segregation is also pronounced: Ca surface segregation is decreased with oxygen pressure reduction.


Epitaxial Thin Films and Heterojunctions of Electron Doped Manganite La1-Xhfxmno3

Epitaxial Thin Films and Heterojunctions of Electron Doped Manganite La1-Xhfxmno3

Author: Libin Jin

Publisher:

Published: 2017-01-26

Total Pages:

ISBN-13: 9781361025710

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This dissertation, "Epitaxial Thin Films and Heterojunctions of Electron Doped Manganite La1-xHfxMnO3" by Libin, Jin, 靳立彬, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled EPITAXIAL THIN FILMS AND HETEROJUNCTIONS OF ELECTRON DOPED MANGANITE La Hf MnO 1-x x 3 Submitted by Jin Libin For the Degree of Master of Philosophy at The University of Hong Kong in October 2015 The strong electron correlated system like perovskite oxides in transition metal oxides have been studied for many years. Most efforts have been focused mainly 3+ 4+ on the hole-doped manganites with Mn /Mn double exchange interaction. Recently, the tetravalent ions doping has attracted considerable attention to make electron doping LaMnO compounds. Such electron-doped manganites may be applied for fabrication of all-manganites devices potentially. The sensitivities to magnetic fields, currents, electric fields, photo illumination and mechanical strain make the electron-doped manganites of great interests for relevant applications. In this thesis, thin films and heterojunctions of tetravalent hafnium doped perovskite manganite La Hf MnO were fabricated. The hafnium shows a 1-x x 3 unique tetravalent state as well as an ion radius closed to trivalent lanthanum ion. These properties make the investigation on La Hf MnO system relatively 1-x x 3 simple and reliable. The structural and physical properties of La Hf MnO (x=0.1, 0.2, 0.3) thin 1-x x 3 films were studied systematically. The crystal structure and epitaxy of La 1- Hf MnO thin films were examined by X-ray diffraction. The temperature x x 3 dependent resistance and magnetization of different samples were investigated in detail. Both temperature dependent resistance and field dependent magnetization indicated the evident transition between paramagnetic and ferromagnetic states. The electronic structures of epitaxial La Hf MnO were measured by X-ray 0.9 0.1 3 Photoelectron Spectroscopy. Both spectrum of Mn 3s and Mn 2p demonstrated 2+ 3+ the composition of Mn /Mn ions. Such evidence strongly suggested the electron-conductive mechanism in La Hf MnO systems. 0.9 0.1 3 The heterojunctions composed of oxygen-deficient SrTiO and 3-δ La Hf MnO thin films have been studied. These heterojunctions demonstrate 0.9 0.1 3 good rectifying characteristics with very low leakage current and high breakdown voltage in a wide temperature range. X-ray diffraction and electron backscattering diffraction measurements reveal that both SrTiO and La Hf MnO layers 3-δ 0.9 0.1 3 have single crystal nature and [001]-orientation. Transmission electron microscope images show an excellent epitaxial growth of SrTiO and 3-δ La Hf MnO layers. Such all-oxides junctions utilizing the bi-layer 0.9 0.1 3 heterostructure may be applied in microelectronic devices. The n-i-p heterojunctions have been fabricated by depositing an n-type La Hf MnO layer on p-type Si with a thin SrTiO intermediate layer. These 0.9 0.1 3 3 junctions exhibit excellent rectifying properties for temperature from 20 K to 300 K. Under illumination of 630 nm light a remarkable photocurrent has been observed. The photosensitivity is over 1200% under -3 V bias and illumination of the light at room temperature, demonstrating very a pronounced photocurrent effect. The injection of photo-carriers could be responsible for the observed phenomenon. The obtained results in this thesis demonstrate the electron-conductive mechanism in La Hf MnO system. The La Hf MnO based heterojunctions 1-x x 3 0.9 0.1 3 show remarkable characteristics and may


Controlling Octahedral Rotations in a Perovskite Via Strain Doping

Controlling Octahedral Rotations in a Perovskite Via Strain Doping

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Published: 2016

Total Pages:

ISBN-13:

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The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film can be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. Lastly, these results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.


The Effect of Epitaxial Strain and R3+ Magnetism on the Interfaces Between Polar Perovskites and SrTiO3

The Effect of Epitaxial Strain and R3+ Magnetism on the Interfaces Between Polar Perovskites and SrTiO3

Author: Mark Charles Monti

Publisher:

Published: 2011

Total Pages: 310

ISBN-13:

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We have embarked on a systematic study of novel charge states at oxide interfaces. We have performed pulsed laser deposition (PLD) growth of epitaxial oxide thin films on single crystal oxide substrates. We studied the effects of epitaxial strain and rare-earth composition of the metal oxide thin films. We have successfully created TiO2 terminated SrTiO3 (STO) substrates and have grown epitaxial thin films of LaAlO3 (LAO), LaGaO3 (LGO), and RAlO3 on STO using a KrF pulsed excimer laser. Current work emphasizes the importance of understanding the effect of both epitaxial strain and R3+ magnetism on the interface between RAlO3 and STO. We have demonstrated that the interfaces between LAO/STO and LGO/STO are metallic with carrier concentrations of 1.1 x 1014 cm[superscript -2] and 4.5 x 1014 cm[superscript -2], respectively. Rare-earth aluminate films, RAlO3, with R = Ce, Pr, Nd, Sm, Eu, Gd, and Tb, were also grown on STO. Conducting interfaces were found for R = Pr, Nd and Gd, and the results indicate that for R [does not equal] La the magnetic nature of the R3+ ion causes increased scattering with decreasing temperature that is modeled by the Kondo effect. Epitaxial strain between the polar RAlO3 films and STO appears to play a crucial role in the transport properties of the metallic interface, where a decrease in the R3+ ion size causes an increase in sheet resistance and an increase in the onset temperatures for increased scattering.


Growth Mechanism and Interface Effects on Microstructure of Perovskite-type Barium Titanate-based Epitaxial Films

Growth Mechanism and Interface Effects on Microstructure of Perovskite-type Barium Titanate-based Epitaxial Films

Author: Jie He

Publisher:

Published: 2012

Total Pages:

ISBN-13:

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This work was motivated and focused on the growth mechanism, microstructures and interfaces of barium titanate, BaTiO3 (BTO), based epitaxial thin films. Transimission electron microscopy (TEM), high resolution TEM (HRTEM), electron diffraction (ED) have been mainly employed in this study for microstructure investigations of BTO-based epitaxial thin films with the assistance of other materials characterization methods, such as X-ray diffraction (XRD), atomic force microscopy (AFM), Nanoindentation testing, etc. As a basic studying model, epitaxial BTO films were first deposited on the (001) MgO substrate using RF magnetron sputtering to provide fundamental knowledge of the film growth for BTO based thin films. The epitaxial BTO films show a tetragonal crystal structure (a = 4.02 Å and c = 4.11 Å) with epitaxial nanodomains induced from the rough film/substrate interface due to the modification of the substrate surface characteristics (steps, terraces, and kinks) during the deposition process. Two new phases of - calculus [gamma]y (Ba10TiO26) and Hß (BaTi8O24) were formed on the MgO substrate using RF magnetron sputtering. The atomic structures of the two new phases were determined and examined. The [gamma]y phase has a monoclinic structure, Cm, a=16.49 Å̊̊, b=8.94 Å, c=3.94 Å, y=77°. The Hß phase has a monoclinic structure, Cm, a = 17.88̊Å̊, b = 7.21Å, c = 3.94 Å̊̊̊, y =82°. Both [gamma]y and Hß phases have four different oriented domains. The orientation relationship between domains and MgO substrate is discussed. Initail study shows that these new phases possess novel and interesting properties. The doped BTO films with different dopant (Sr2 and Zr4) fabricated using pulsed laser deposition (PLD) have been studied for doping effects, interface effects and film growth mechanism. The (Ba, Sr)TiO3 (BST) epitaxial films grown on 1.2° and 5.3° miscut substrates consist of lager commensurate domains, and correspondly show higher dielectric constant and dielectric tunability, and lower average modulus and hardness than those of the films grown on the 3.5° miscut substrate. The results suggest that the differences on the interfacial structure have a tremendous effect on the properties of the films. The investigation on epitaxial Ba(Zr, Ti)O3 (BZT) and 2% Mn doped Ba(Zr, Ti)O3 (Mn:BZT) thin films grown on MgO substrate revealed the formation of twin-coupled domains on the epilayer by sharing their {111}/{110} planes as common planes. The structure evolution from epilayer to nanopillars is accomplished by alternatively introducing {111} and {110} twin boundaries, resulting in gradual shrinking or enlarging of the lateral size of the epitaxial grains/twin coupled nanopillars. The formations of twin domains, sharing planes and structure transition mechasim have been discussed in detail. Eventually, the microstructures and layer interfaces of [Mn:BZT//Mn:BST]N multilayer films consisting of 2% Mn doped (Ba, Sr)TiO3 (Mn:BST) and Mn:BZT layers on MgO (001) substrates with various deposition rates, deposition period numbers N were studied to provide an integral view of the formation of multilayer films in BTO system. All the [Mn:BZT//Mn:BST]N multilayer films present epitaxial quality and induced {111}/{110} twin-coupled domains initially formed at different film thickness/layers. The film/substrate interface has an important role for the formation of twin domains and the proportion of twin domain structures in the entire films. The layer interfaces between Mn:BST and Mn:BZT with period compression and extension strains were observed and discussed. The microstructure evolution and structure-related nano-mechanical properties of the multilayer films have been systematically investigated.


Atomically Resolved STM Studies of the Perovskite Manganite Thin-film Surfaces

Atomically Resolved STM Studies of the Perovskite Manganite Thin-film Surfaces

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Published: 2009

Total Pages: 100

ISBN-13:

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Perovskite manganites are complex systems in which the structural, electronic, and magnetic properties are strongly coupled - in many cases, non-linearly. A small change in one property (e.g., structure) can produce a large change in other properties (e.g., the electronic state). Conceptually, creating a surface by cleaving a single crystal or growing a thin film provides a controlled way to disturb the coupled system by breaking the symmetry without changing the stoichiometry, which may lead to completely new physical properties. The emerging surface electronic phases can be further enriched by surface reconstructions which often occur due to bond breaking at the surface and also by extrinsic carrier doping from adsorbates as well. While the cleaving method is limited to a small amount of cleavable layered materials, the thin-film growth method, such as laser molecular beam epitaxy (Laser MBE), becomes the most desired technique for the study of surfaces in general. As an example, La1-[subscript x]Ca[subscript x]MnO3, which is one of the most investigated cubic perovskite manganite systems, has a surface that cannot be created by cleaving the bulk but can be prepared by laser MBE. In this dissertation, La1-[subscript x]Ca[subscript x]MnO2 (001) (x = 3/8) thin films grown by laser MBE were studied with a combination of in-situ techniques such as low-energy electron diffraction (LEED) and high-resolution scanning probe microscopy (SPM). Two different electronic conductivities were observed using scanning tunneling spectroscopy (STS) on the thin-film surface. The "atomic" resolution scanning tunneling microscopy (STM) images revealed that the two different conductivities come from two reconstructed surfaces, (1 x 1) and ([square root]2 x [square root]2)R45°, respectively. The (1 x 1) and ([square root]2 x [square root]2)R45° reconstructions were found to be reversible by oxygen adsorption/desorption, and as a result, the conductivity of the surface can be tuned from metallic to insulating by controlling the oxygen adsorption. Further investigations revealed the existence of a surface structure transition driven by the film thickness. The (1 x 1) surface without oxygen adsorption actually has specific superstructures; it changes from c(2 x 4) to (3[square root]2 x 4[square root]2)R45° with a critical thickness of 14 ML associated with an extensive strain induced by the substrate. The discoveries of the unexpected surface structural and electronic transitions revealed in this dissertation open up a new direction for exploring the functionality relationship at the surfaces of complex transition-metal compound thin films.


Perovskite Oxide Thin Film Growth, Characterization, and Stability

Perovskite Oxide Thin Film Growth, Characterization, and Stability

Author: Andrew Izumi

Publisher:

Published: 2015

Total Pages:

ISBN-13: 9781339260808

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Studies into a class of materials known as complex oxides have evoked a great deal of interest due to their unique magnetic, ferroelectric, and superconducting properties. In particular, materials with the ABO3 perovskite structure have highly tunable properties because of the high stability of the structure, which allows for large scale doping and strain. This also allows for a large selection of A and B cations and valences, which can further modify the material's electronic structure. Additionally, deposition of these materials as thin films and superlattices through techniques such as pulsed laser deposition (PLD) results in novel properties due to the reduced dimensionality of the material. The novel properties of perovskite oxide heterostructures can be traced to a several sources, including chemical intermixing, strain and defect formation, and electronic reconstruction. The correlations between microstructure and physical properties must be investigated by examining the physical and electronic structure of perovskites in order to understand this class of materials. Some perovskites can undergo phase changes due to temperature, electrical fields, and magnetic fields. In this work we investigated Nd0.5Sr0.5MnO3 (NSMO), which undergoes a first order magnetic and electronic transition at T=158K in bulk form. Above this temperature NSMO is a ferromagnetic metal, but transitions into an antiferromagnetic insulator as the temperature is decreased. This rapid transition has interesting potential in memory devices. However, when NSMO is deposited on (001)-oriented SrTiO3 (STO) or (001)-oriented (LaAlO3)0.3-(Sr2AlTaO6)0.7 (LSAT) substrates, this transition is lost. It has has been reported in the literature that depositing NSMO on (110)-oriented STO allows for the transition to reemerge due to the partial epitaxial growth, where the NSMO film is strained along the [001] surface axis and partially relaxed along the [11̄0] surface axis. This allows the NSMO film enough freedom of movement to undergo a shear strain along the [11̄0] axes, allowing the NSMO film to switch phases. It was found that the desired magnetic and electrical properties were closely tied to the structural properties, which were highly sensitive to the precise growth conditions. These perovskite oxides can be further geometrically constrained by patterning, resulting in additional novel magnetic and electrical properties. One such method of patterning involves implanting Ar into a film to locally destabilize the ordered perovskite structure, therefore suppress the magnetic and electrical properties. However, to fully integrate this technique into devices which require multi-planar processes, the ability for a patterned perovskite film to withstand high temperature anneals is crucial in creating more advanced structures. The stability of Ar-implanted La0.7Sr0.3MnO3 (LSMO) thin films was studied upon annealing at 400°C, 500°C, and 600°C. The LSMO retained its amorphous structure with little ferromagnetism after a 400°C anneal, but anneals at 500°C and 600°C resulted in partial recrystallization and a return of the ferromagnetic properties. This recrystallized film displayed semiconducting properties with a lower Curie temperature than the as deposited film. The deposition of an La0.7Sr0.3FeO3 (LSFO) film onto an Ar implanted LSMO film at 400°C caused the LSMO film to almost fully recrystallize, suggesting that the deposition process also recrystallizes the Ar-implanted film. In conclusion, two perovskites films were explored in this thesis. NSMO films proved to be very sensitive to growth conditions, and Ar-implanted LSMO films quickly recrystallized past 400°C or a subsequent film deposition. These studies provide useful information on the structural and electronic transformations these films go through during heat treatment and strain engineering.


Functional Complex Oxide Thin Films and Related Superlattices Grown Via Pulsed Laser Deposition

Functional Complex Oxide Thin Films and Related Superlattices Grown Via Pulsed Laser Deposition

Author: Joseph A. Cianfrone

Publisher:

Published: 2011

Total Pages:

ISBN-13:

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ABSTRACT: Oxide electronics offer a wide array of interesting properties, including ferromagnetism, ferroelectricity and superconductivity. This dissertation investigates the transport, magnetic, and structural properties of several perovskite and spinel material systems, with particular interest in their manipulation at the nanoscale through the growth of functional heterostructures. Spinel phase ZnCo2O4 is investigated as a ferromagnetic semiconductor whose carrier type changes with oxygen concentration. The perovskite system of K(Ta, Nb)O3 is investigated for its interesting properties as a solid solution which exhibits a ferroelectric transition dependent on composition. Its thin film epitaxial growth modes are investigated via reflection high energy electron diffraction, with particular attention paid to the volatile potassium ion. Superlattices of K(Ta, Nb)O3 and SrTiO3 are also investigated for the possibility of dielectric enhancement and conductive interfaces. The multiferroic properties of BaFeO3 K(Ta, Nb)O3 superlattices are investigated, with particular attention paid to the role of magnetoelectric coupling and strain as stabilizing mechanisms.