Hybrid oxide molecular beam epitaxy (hMBE), a thin-film deposition technique in which transition metal cations are delivered using a metal-organic precursor, has emerged as the state-of-the-art approach to the synthesis of electronic-grade complex oxide films with a stoichiometric growth window. However, numerous questions remain regarding the chemical mechanisms of the growth process and the surface properties of the resulting films. To examine these properties, thin film SrTiO$_{3}$ (STO) was prepared by hMBE using a titanium tetraisopropoxide (TTIP) precursor for Ti delivery and an elemental Sr source on annealed STO and Nb-doped STO substrates with varying TTIP:Sr flux ratios to examine the conditions for the reported stoichiometric growth window. The films were transferred in vacuo to an x-ray photoelectron spectroscopy system to study the surface elemental composition. Samples were examined using x-ray diffraction to compare our surface sensitive results with previously reported measurements of the bulk of the films in the literature. Ex situ studies by atomic force microscopy, scanning tunneling microscopy and low energy electron microscopy confirmed the presence of surface reconstructions and an Ehrlich-Schwoebel barrier consistent with an A-site SrO termination. We find that a surface exhibiting a mixture of SrO and TiO$_{2}$ termination, or a full SrO termination is necessary to obtain stoichiometric adsorption-controlled growth. These results indicate that surface Sr is necessary to maintain chemical equilibrium for stoichiometric growth during the hMBE process, which is important for the design of future interfacial systems using this technique.
We investigate the effect of the laser parameters of pulsed laser deposition on the film stoichiometry and electronic properties of LaAlO_3/SrTiO_3 (001) heterostructures. The La/Al ratio in the LaAlO_3 films was varied over a wide range from 0.88 to 1.15, and was found to have a strong effect on the interface conductivity. In particular, the carrier density is modulated over more than two orders of magnitude. The film lattice expansion, caused by cation vacancies, is found to be the important functional parameter. These results can be understood to arise from the variations in the electrostat…
Controlling the surface structure on the atomic scale is a major difficulty for most transition metal oxides; this is especially true for the ternary perovskites. The influence of surface stoichiometry on the atomic structure of the SrTiO$_3$(001) surface was examined with scanning tunneling microscopy, low-energy electron diffraction, low-energy He$^+$ ion scattering (LEIS), and X-ray photoelectron spectroscopy (XPS). Vapor deposition of 0.8 monolayer (ML) strontium and 0.3 ML titanium, with subsequent annealing to 850 °C in 4 $\times$ 10$^{-6}$ mbar O$_2$, reversibly switches the surface bet…
In many transition metal oxides (TMOs), oxygen stoichiometry is one of the most critical parameters that plays a key role in determining the structural, physical, optical, and electrochemical properties of the material. However, controlling the growth to obtain high quality single crystal films having the right oxygen stoichiometry, especially in a high vacuum environment, has been viewed as a challenge. In this work, we show that through proper control of the plume kinetic energy, stoichiometric crystalline films can be synthesized without generating oxygen defects, even in high vacuum. We us…
We report on the fabrication of conducting interfaces between LaAlO$_3$ and SrTiO$_3$ by 90$^o$ off-axis sputtering in an Ar atmosphere. At a growth pressure of 0.04 mbar the interface is metallic, with a carrier density of the order of $10^{13}$ cm$^{-2}$ at 3 K. By increasing the growth pressure, we observe an increase of the out-of-plane lattice constants of the LaAlO$_3$ films while the in-plane lattice constants do not change. Also, the low-temperature sheet resistance increases with increasing growth pressure, leading to an insulating interface when the growth pressure reaches 0.10 mbar.…
Control of thin film stoichiometry is of primary relevance to achieve desired functionality. Pulsed laser deposition ablating from binary-oxide targets (sequential deposition) can be applied to precisely control the film composition, offsetting the importance of growth conditions on the film stoichiometry. In this work, we demonstrate that the cation stoichiometry of SrTiO$_3$ thin films can be finely tuned by sequential deposition from SrO and TiO$_2$ targets. Homoepitaxial SrTiO$_3$ films were deposited at different substrate temperatures and Ti/Sr pulse ratios, allowing the establishment of…
Cryogenic scanning tunneling microscopy is employed to investigate the stoichiometry and defects of epitaxial FeSe thin films on SrTiO3(001) substrates under various post-growth annealing conditions. Low-temperature annealing with an excess supply of Se leads to formation of Fe vacancies and superstructures, accompanied by a superconductivity (metal)-to-insulator transition in FeSe films. By contrast, high-temperature annealing could eliminate the Fe vacancies and superstructures, and thus recover the high-temperature superconducting phase of monolayer FeSe films. We also observe multilayer Fe…
We present a comprehensive first-principles study of the electronic charge redistribution in atomically sharp LaAlO$_3$/SrTiO$_3$(001) heterointerfaces of both n- and p-types allowing for non-stoichiometric composition. Using two different computational methods within the framework of the density functional theory (linear combination of atomic orbitals and plane waves) we demonstrate that conducting properties of LaAlO$_3$/SrTiO$_3$(001) heterointerfaces strongly depend on termination of LaAlO$_3$ (001) surface. We argue that both the polar "catastrophe" and the polar distortion scenarios may …
Hard x-ray photoelectron spectroscopy (HAXPES) and variable kinetic energy x-ray photoelectron spectroscopy (VKE-XPS) analyses have been performed on 10 unit cell La$_{(1-δ)}$Al$_{(1+δ)}$O$_3$ films, with La:Al ratios of 1.1, 1.0, and 0.9, deposited on SrTiO$_3$. Of the three films, only the Al-rich film was known to have a conductive interface. VKE-XPS, coupled with maximum entropy analysis, shows significant differences in the compositional depth profile between the Al-rich, the La-rich, and stoichiometric films; significant La enrichment at the interface is observed in the La-rich and stoic…
We have investigated the atomically-resolved substrate and homoepitaxial thin film surfaces of SrTiO3(001) using low-temperature scanning tunneling microscopy/spectroscopy (STM/STS) combined with pulsed laser deposition (PLD). It was found that annealing at 1000 oC in an oxygen partial pressure of 1*10-6 Torr, which is a typical annealing treatment for the preparation of SrTiO3 substrates, unexpectedly resulted in a disordered surface on an atomic scale. In contrast, homoepitaxial SrTiO3 thin films grown on this disordered substrate exhibited (2*2) surface reconstructions. The differential con…
Antiphase domain boundaries (APDBs) in the ($n \times 1$)($n=4,5$) reconstructions of the SrTiO$_3$(110) surface were studied with scanning tunneling microscopy, x-ray photoemission spectroscopy, and density functional theory (DFT) calculations. Two types of APDBs form on each reconstruction; they consist of Ti$_x$O$_y$ vacancy clusters with a specific stoichiometry. The presence of these clusters is controlled by the oxygen pressure during annealing. The structural models of the vacancy clusters are resolved with DFT, which also shows that their relative stability depends on the chemical pote…
Perovskite insulator SrTiO3 is expected to be applied to the next generation of electronic and photonic devices as high-k capacitors and photocatalysts. However, reproducible growth of highly insulating stoichiometric SrTiO3 films remains challenging due to the difficulty of the precise stoichiometry control in perovskite oxide films. Here, to grow stoichiometric SrTiO3 thin films by fine-tuning multiple growth conditions, we developed a new Bayesian optimization (BO)-based machine learning method that encourages the exploration of the search space by varying the prior mean to get out of subop…
We have investigated the growth of BaTiO3 thin films deposited on pure and 1% Nb-doped SrTiO3(001) single crystals using atomic oxygen assisted molecular beam epitaxy (AO-MBE) and dedicated Ba and Ti Knudsen cells. Thicknesses up to 30 nm were investigated for various layer compositions. We demonstrate 2D growth and epitaxial single crystalline BaTiO3 layers up to 10 nm before additional 3D features appear; lattice parameter relaxation occurs during the first few nanometers and is completed at »10 nm. The presence of a Ba oxide rich top layer that probably favors 2D growth is evidenced for wel…
We show that reflection high-energy electron diffraction (RHEED) can be used as a highly sensitive tool to track surface and resulting film stoichiometry in adsorption-limited molecular beam epitaxy of (001) SrTiO3 thin films. Even under growth conditions that yield films with a lattice parameter that is identical to that of stoichiometric bulk crystals within the detection limit of high-resolution x-ray diffraction (XRD), changes in surface reconstruction occur from (1x1) to (2x1) to c(4x4) as the equivalent beam pressure of the Ti metalorganic source is increased. These surface reconstructio…
We have investigated the properties of interfaces between LaAlO3 films grown on SrTiO3 substrates singly terminated by TiO2. We used RF sputtering in a high-pressure oxygen atmosphere. The films are smooth, with flat surfaces. Transmission Electron Microscopy shows atomically sharp and continuous interfaces while EELS measurements show some slight intermixing. The elemental ratio of La to Al measured by EDX is found to be 1.07. Importantly, we find these interfaces to be non-conducting, indicating that the sputtered interface is not electronically reconstructed in the way reported for films gr…
The surface structure of SrTiO3(001) thin films homoepitaxially grown by PLD in step-flow mode was characterized using low temperature STM. It was found that one-dimensional (1D) TiOx-based nanostructures were formed on the thin film surface and their density increased with increasing thin film thickness. Most of the 1D nanostructures disappeared after a post-deposition annealing, indicating that this structure is metastable due to the nonequilibrium growth mode. The resulting surface after annealing exhibited similar features to that of a thinner film, having a domain structure with (2x1) and…
Comparison between single- and the poly-crystalline structures provides essential information on the role of long-range translational symmetry and grain boundaries. In particular, by comparing single- and poly-crystalline transition metal oxides (TMOs), one can study intriguing physical phenomena such as electronic and ionic conduction at the grain boundaries, phonon propagation, and various domain properties. In order to make an accurate comparison, however, both single- and poly-crystalline samples should have the same quality, e.g., stoichiometry, crystallinity, thickness, etc. Here, by stu…
The two-dimensional electron gas occurring between the band insulators SrTiO$_3$ and LaAlO$_3$ continues to attract considerable interest, due to the possibility of dynamic control over the carrier density, and the ensuing phenomena such as magnetism and superconductivity. The formation of this conducting interface is sensitive to the growth conditions, but despite numerous investigations, there are still questions about the details of the physics involved. In particular, not much is known about the electronic structure of the growing LaAlO$_3$ layer at the growth temperature (around 800 $^o$C…
Among the class of strongly-correlated oxides, La1-xSrxMnO3 $-$ a half metallic ferromagnet with a Curie temperature above room temperature $-$ has sparked a huge interest as a functional building block for memory storage and spintronic applications. In this respect, defect engineering has been in the focus of a long-standing quest for fabricating LSMO thin films with highest quality in terms of both structural and magnetic properties. Here, we discuss the correlation between structural defects, such as oxygen vacancies and impurity islands, and magnetism in La0.74Sr0.26MnO3/SrTiO3 (LSMO/STO) …
In this Thesis, a study of the electronic structure of two Ti-based oxide systems, TiO2 thin films and the ultra-thin LaAlO3-SrTiO3 (LAO-STO) heterojunctions, is given. A weak room-temperature ferromagnetism (FM) has been detected in slightly reduced TiO2 thin film and in other oxides; as these materials are insulating closed-shell systems, this phenomenon has been classified as "d0 magnetism". Since this magnetism could be related to the growth process and to the presence of defects (oxygen vacancies, VO), an analysis of Ti electronic states (especially of Ti3+ energy levels) is mandatory. Th…
Effects of X-ray irradiation on the electronic structure of LaAlO$_3$/SrTiO$_3$ (LAO/STO) samples, grown at low oxygen pressure and post-annealed ex-situ till recovery of their stoichiometry, were investigated by soft-X-ray ARPES. The irradiation at low sample temperature below ~100K creates oxygen vacancies (VOs) injecting Ti t2g-electrons into the interfacial mobile electron system (MES). At this temperature the oxygen out-diffusion is suppressed, and the VOs are expected to appear mostly in the top STO layer. However, we observe a pronounced three-dimensional (3D) character of the X-ray gen…
The intrinsic magnetic state (ferromagnetic or antiferromagnetic) of ultra-thin LaMnO$_3$ films on the mostly used SrTiO$_3$ substrate is a long-existing question under debate. Either strain effect or non-stoichiometry was argued to be responsible for the experimental ferromagnetism. In a recent experiment [Science \textbf{349}, 716 (2015)], one more mechanism, namely the self-doping due to polar discontinuity, was argued to be the driving force of ferromagnetism beyond the critical thickness. Here systematic first-principles calculations have been performed to check these mechanisms in ultra-…
The epitaxial growth of functional materials using a substrate with a graphene layer is a highly desirable method for improving structural quality and obtaining free-standing epitaxial nano-membranes for scientific study, applications, and economical reuse of substrates. However, the aggressive oxidizing conditions typically employed to grow epitaxial perovskite oxides can damage graphene. Here, we demonstrate a technique based on hybrid molecular beam epitaxy that does not require an independent oxygen source to achieve epitaxial growth of complex oxides without damaging the underlying graphe…
Stoichiometric Epitaxial Strontium Titanate Thin Films on Silicon by High-Temperature Sr Segregation
Imec；Department of Materials Engineering (MTM), KU Leuven（荷语鲁汶大学材料工程系）；Physics Department, Jean Monnet University（圣艾蒂安让·穆内大学物理系）；Department of Information Technology (INTEC), Photonics Research Group, Ghent University（根特大学信息与科技学院光子学研究组）
Understanding and manipulating properties emerging at a surface or an interface require a thorough knowledge of structure-property relationships. We report a study of a prototype oxide system, La2/3Sr1/3MnO3 grown on SrTiO3(001), by combining in-situ angle-resolved x-ray photoelectron spectroscopy, ex-situ x-ray diffraction, and scanning transmission electron microscopy/spectroscopy with electric transport measurements. We find that La2/3Sr1/3MnO3 films thicker than 20 unit cells (u.c.) exhibit a universal behavior with no more than one u.c. intermixing at the interface but at least 3 u.c. of …
We investigated the structural and magnetic properties of bare SrRuO$_3$ (SRO) ultra-thin films and SrRuO$_3$/SrIrO$_3$/SrZrO$_3$ (SRO/SIO/SZO: RIZ) trilayer heterostructures between 10 K and 80 K, by comparing macroscopic data using magneto-optical Kerr effect (MOKE) and magneto-transport (anomalous Hall effect: AHE), with nanoscale fingerprints when applying non-contact scanning force microscopy (nc-SFM) and magnetic force microscopy (MFM). SRO and RIZ ultra-thin films were epitaxially grown at 650C onto vicinal SrTiO$_3$ (100) single-crystalline substrates to a nominal thickness of 4 and 4/…
The use of oxide materials in oxide electronics requires their controlled epitaxial growth. Recently, it was shown that Reflection High Energy Electron Diffraction (RHEED) allows to monitor the growth of oxide thin films even at high oxygen pressure. Here, we report the sub-unit cell molecular or block layer growth of the oxide materials Sr2RuO4, MgO, and magnetite using Pulsed Laser Deposition (PLD) from stoichiometric targets. Whereas for perovskites such as SrTiO3 or doped LaMnO3 a single RHEED intensity oscillation is found to correspond to the growth of a single unit cell, in materials wh…
We have grown epitaxial thin films of multiferroic BiMnO$_3$ using pulsed laser deposition. The films were grown on SrTiO$_3$ (001) substrates by ablating a Bi-rich target. Using x-ray diffraction we confirmed that the films were epitaxial and the stoichiometry of the films was confirmed using Auger electron spectroscopy. The films have a ferromagnetic Curie temperature ($T_C$) of 85$\pm$5 K and a saturation magnetization of 1 $μ_B$/Mn. The electric polarization as a function of electric field ($P-E$) was measured using an interdigital capacitance geometry. The $P-E$ plot shows a clear hystere…
An experimental study was conducted on controlling the growth mode of La0.7Sr0.3MnO3 thin films on SrTiO3 substrates using pulsed laser deposition (PLD) by tuning growth temperature, pressure and laser fluence. Different thin film morphology, crystallinity and stoichiometry have been observed depending on growth parameters. To understand the microscopic origin, the adatom nucleation, step advance processes and their relationship to film growth were theoretically analyzed and a growth diagram was constructed. Three boundaries between highly and poorly crystallized growth, 2D and 3D growth, stoi…
Ternary chalcogenides such as the parkerites and shandites are a broad class of materials exhibiting rich diversity of transport and magnetic behavior as well as an array of topological phases including Weyl and Dirac nodes. However, they remain largely unexplored as high-quality epitaxial thin films. Here, we report the self-regulated growth of thin films of the strong spin-orbit coupled superconductor Pd3Bi2Se2 on SrTiO3 by molecular beam epitaxy. Films are found to grow in a self-regulated fashion, where, in excess Se, the temperature and relative flux ratio of Pd to Bi controls the formati…
Crystal surfaces are sensitive to the surrounding environment, where atoms left with broken bonds reconstruct to minimize surface energy. In many cases, the surface can exhibit chemical properties unique from the bulk. These differences are important as they control reactions and mediate thin film growth. This is particularly true for complex oxides where certain terminating crystal planes are polar and have a net dipole moment. For polar terminations, reconstruction of atoms on the surface is the central mechanism to avoid the so called polar catastrophe. This adds to the complexity of the re…
We investigate structural and transport properties of highly Ru-deficient SrRu0.7O3 thin films prepared by molecular beam epitaxy on (001) SrTiO3 substrates. To distinguish the influence of the two types of disorders in the films, Ru vacancies within lattices and disorders near the interface, SrRu0.7O3 thin films with various thicknesses (t = 1-60 nm) were prepared. It was found that the influence of the former dominates the electrical and magnetic properties when t > 5-10 nm, while that of the latter does when t < 5-10 nm. Structural characterizations revealed that the crystallinity, in terms…
