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 electrostatic boundary conditions, and their resolution, with stoichiometry.
We study the decay of interface induced structural and electronic relaxation effects in epitaxial LaAlO3/SrTiO3 heterostructures. The results are based on first-principles band structure calculations for a multilayer configuration with an ultrathin LaAlO3 layer sandwiched between bulk-like SrTiO3 layers. We carry out the structure optimization for the heterointerface and investigate the electronic states of the conducting interface layer, which is found to extend over two SrTiO3 unit cells. The decay of atomic displacements is analyzed as a function of the distance to the interface, and the re…
We have studied the electronic structure at the heterointerface between the band insulators LaAlO$_3$ and SrTiO$_3$ using $in situ$ photoemission spectroscopy. Our experimental results clearly reveal the formation of a notched structure on the SrTiO$_3$ side due to band bending at the metallic LaAlO$_3$/TiO$_2$-SrTiO$_3$ interface. The structure, however, is absent at the insulating LaAlO$_3$/SrO-SrTiO$_3$ interface. The present results indicate that the metallic states originate not from the charge transfer through the interface on a short-range scale but from the accumulation of carriers on …
We present a first-principles study of the electronic structures and properties of ideal (atomically sharp) LaAlO3/SrTiO3 (001) heterointerfaces and their variants such as a new class of quantum well systems. We demonstrate the insulating-to-metallic transition as a function of the LaAlO3 film thickness in these systems. After the phase transition, we find that conduction electrons are bound to the n-type interface while holes diffuse away from the p-type interface, and we explain this asymmetry in terms of a large hopping matrix element that is unique to the n-type interface. We build a tight…
Using a combination of vertical transport measurements across and lateral transport measurements along the LaAlO$_{3}$/SrTiO$_{3}$ heterointerface, we demonstrate that significant potential barrier lowering and band bending are the cause of interfacial metallicity. Barrier lowering and enhanced band bending extends over 2.5 nm into LaAlO$_{3}$ as well as SrTiO$_{3}$. We explain origins of high-temperature carrier saturation, lower carrier concentration, and higher mobility in the sample with the thinnest LaAlO$_{3}$ film on a SrTiO$_{3}$ substrate. Lateral transport results suggest that parasi…
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.…
A set of LaAlO3/SrTiO3 (LAO-STO) interfaces has been probed by X-ray photoemission spectroscopy in order to contrast and compare the effects of LAO overlayer thickness and of the growth conditions on the electronic properties of these heterostructures. These effects are tracked by considering the band-offset and the density of Ti3+ states, respectively. It is shown that the dominant effects on the local electronic properties are determined by the O2 partial pressure during the growth. In particular, a low P(O2) yields Ti3+ states with higher density and lower binding energy as compared to the …
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 …
We investigated \LAO\ - \STO\ heterointerfaces grown either in oxygen rich or poor atmosphere by soft x-ray spectroscopy. Resonant photoemission across the Ti L$_{2,3}$ absorption edge of the valence band and Ti 2p core level spectroscopy directly monitor the impact of oxygen treatment upon the electronic structure. Two types of Ti$^{3+}$ related charge carriers are identified. One is located at the Fermi energy and related to the filling of the \STO\ conduction band. It appears for low oxygen pressure only. The other one is centered at E$_{B}$ $\approx$ 1 eV and independent of the oxygen pres…
Emergent phenomena, including superconductivity and magnetism, found in the two-dimensional electron liquid (2-DEL) at the interface between the insulators LaAlO3 and SrTiO3 distinguish this rich system from conventional two-dimensional electron gases at compound semiconductor interfaces. The origin of this 2-DEL, however, is highly debated with focus on the role of defects in the SrTiO3 while the LaAlO3 has been assumed perfect. Our experiments and first principles calculations show that the cation stoichiometry of the nominal LaAlO3 layer is key to 2-DEL formation: only Al-rich LaAlO3 result…
SrTiO$_3$ is a superconducting semiconductor with a pairing mechanism that is not well understood. SrTiO$_3$ undergoes a ferroelastic transition at $T=$ 105 K, leading to the formation of domains with boundaries that can couple to electronic properties. At two-dimensional SrTiO$_3$ interfaces, the orientation of these ferroelastic domains is known to couple to the electron density, leading to electron-rich regions that favor out-of-plane distortions and electron-poor regions that favor in-plane distortion. Here we show that ferroelastic domain walls support low energy excitations that are anal…
The confinement of the two dimensional electron gas (2DEG), preferential occupancy of the Ti 3d orbital and strong spin-orbit coupling at the LaAlO$_3$/SrTiO$_3$ interface play a significant role in its emerging properties. Here we report a fourfold oscillation in the anisotropic magneto resistance (AMR) and the observation of planar Hall effect (PHE) at the LaAlO$_3$/SrTiO$_3$ heterointerface. We evaluate the carrier confinement effects on the AMR and find that the fourfold oscillation appears only for the case of 2DEG system while it is twofold for the 3D system. As the fourfold oscillation …
The ability to control materials properties through interface engineering is demonstrated by the appearance of conductivity at the interface of certain insulators, most famously the {001} interface of the band insulators LaAlO$_{3}$ and TiO$_{2}$-terminated SrTiO$_{3}$ (STO). Transport and other measurements in this system show a plethora of diverse physical phenomena. To better understand the interface conductivity, we used scanning superconducting quantum interference device microscopy to image the magnetic field locally generated by current in an interface. At low temperature, we found that…
The transfer of electrons between a solid surface and adsorbed atomic or molecular species is fundamental in natural and synthetic processes, being at the heart of most catalytic reactions and many sensors. In special cases, metallic conduction can be induced at the surface of, for example, Si-terminated SiC1, or mixed-terminated ZnO2, in the presence of a hydrogen adlayer. Generally, only the surface atoms are significantly affected by adsorbates. However, remotely changing electronic states far from the adsorbed layer is possible if these states are electrostatically coupled to the surface. …
We have made very thin films of LaAlO3 on TiO2 terminated SrTiO3 and have measured the properties of the resulting interface in various ways. Transport measurements show a maximum sheet carrier density of 1016 cm-2 and a mobility around 104 cm2 V-1 s-1. In situ ultraviolet photoelectron spectroscopy (UPS) indicates that for these samples a finite density of states exists at the Fermi level. From the oxygen pressure dependence measured in both transport as well as the UPS, we detail, as reported previously by us, that oxygen vacancies play an important role in the creation of the charge carrier…
Electrical transport of a polar heterointerface between two insulating perovskites, KTaO3 and SrTiO3, is studied. It is formed between a thin KTaO3 film deposited on a top of TiO2- terminated (100) SrTiO3 substrate. The resulting (KO)1-(TiO2)0 heterointerface is expected to be hole-doped according to formal valences of K (1+) and Ti (4+). We observed electrical conductivity and mobility in the KTaO3/SrTiO3 similar to values measured earlier in electron-doped LaAlO3/SrTiO3 heterointerfaces. However, the sign of the charge carriers in KTaO3/SrTiO3 obtained from the Hall measurements is negative.…
We report on surface effects on the electronic properties of interfaces in epitaxial LaAlO$_3$/SrTiO$_3$ heterostructures. Our results are based on first-principles electronic structure calculations for well-relaxed multilayer configurations, terminated by an ultrathin LaAlO$_3$ surface layer. On varying the thickness of this layer, we find that the interface conduction states are subject to almost rigid band shifts due to a modified Fermi energy. Confirming experimental data, the electronic properties of heterointerfaces therefore can be tuned systematically by alterating the surface-interfac…
The properties of single-crystal SrTiO$_{3}$ substrates and homoepitaxial SrTiO$_{3}$ films grown by pulsed laser deposition have been compared, in order to understand the loss of interfacial conductivity when more than a critical thickness of nominally homoepitaxial SrTiO$_{3}$ is inserted between a LaAlO$_{3}$ film and a SrTiO$_{3}$ substrate. In particular, the chemical composition and the structure of homoepitaxial SrTiO$_{3}$ investigated by low-energy ion-scattering and surface x-ray diffraction, show that for insulating heterointerfaces, a Sr-excess is present between the LaAlO$_{3}$ an…
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 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…
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…
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…
SrTiO$_3$-based heterointerfaces support quasi-two-dimensional (2D) electron systems that are analogous to III-V semiconductor heterostructures, but also possess superconducting, magnetic, spintronic, ferroelectric, and ferroelastic degrees of freedom. Despite these rich properties, the relatively low mobilities of 2D complex-oxide interfaces appear to preclude ballistic transport in 1D. Here we show that the 2D LaAlO$_3$/SrTiO$_3$ interface can support quantized ballistic transport of electrons and (non-superconducting) electron pairs within quasi-1D structures that are created using a well-e…
The two-dimensional metal forming at the interface between an oxide insulator and SrTiO3 provides new opportunities for oxide electronics. However, the quantum Hall effect, one of the most fascinating effects of electrons confined in two dimensions, remains underexplored at these complex oxide heterointerfaces. Here, we report the experimental observation of quantized Hall resistance in a SrTiO3 heterointerface based on the modulation-doped amorphous-LaAlO$_{3}$/SrTiO$_{3}$ heterostructure, which exhibits both high electron mobility exceeding 10000 cm$^{2}$/Vs and low carrier density on the or…
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-…
We report the results of a combined experimental and theoretical study on nonstoichiometric CrN1+d thin films grown by reactive magnetron sputtering on c-plane sapphire, MgO (100) and LaAlO3 (100) substrates in a Ar/N2 gas mixture using different percentage of N2. There is a transition from n-type to p-type behavior in the layers as a function of nitrogen concentration varying from 48 at. % to 52 at. % in CrN films. The compositional change follows a similar trend for all substrates, with a N/Cr ratio increasing from approximately 0.7 to 1.06-1.10 by increasing percentage of N2 in the gas flow…
