Felix Gunkel

Influence of charge compensation mechanisms on the sheet electron density at conducting LaAlO3/SrTiO3-interfaces

The equilibrium conductance of LaAlO3/SrTiO3 (LAO/STO)-heterointerfaces was investigated at high temperatures (950?K-1100?K) as a function of ambient oxygen partial pressure (pO2). Metallic LAO/STO-interfaces were obtained for LAO grown on STO single crystals as well as on STO-buffered (La,Sr)(Al,Ta)O3 substrates. For both structures, the high temperature sheet carrier density nS of the LAO/STO-interface saturates at a value of about 1?×?1014?cm?2 for reducing conditions, which indicates the presence of interfacial donor states. A significant decrease of nS is observed at high oxygen partial pressures. According to the defect chemistry model of donor-doped STO, this behavior for oxidizing conditions can be attributed to the formation of Sr-vacancies as charge compensating defects.

High temperature conductance characteristics of LaAlO3/SrTiO3-heterostructures under equilibrium oxygen atmospheres

The interface conductance of LaAlO3/SrTiO3 heterostructures was investigated under high temperature oxygen equilibrium. The dependence of the heterostructure’s conductance on oxygen partial pressure (from 10−22 to 1 bar) and temperature (800 to 1100 K) was compared to the characteristic of SrTiO3 single crystals, which is described in terms of a defect chemistry model. Up to 950 K the equilibrated heterostructures reveal an additional influence of a metallic-like conduction path with a very slight dependence on the oxygen partial pressure. Donor-type interface states which may result from either lattice distortions or A-site cation intermixing during processing are discussed as a possible origin for the exceptional interface conduction of LaAlO3/SrTiO3 heterostructures.

Stoichiometry dependence and thermal stability of conducting NdGaO3/SrTiO3 heterointerfaces

The structural and electrical properties of conducting NdGaO3/SrTiO3 (NGO/STO) heterostructures grown at various deposition temperatures were investigated. X-ray diffraction and X-ray photoelectron spectroscopy reveal a strong impact of the growth temperature on both crystallinity and cation stoichiometry of the NGO thin films. This stoichiometry variation significantly affects the electrical properties of the NGO/STO interface. High temperature conductance measurements under oxygen equilibrium conditions show a distinct conductance contribution of the NGO/STO interface up to 1000 K and exclude a conduction effect caused by a mere reduction of the STO substrate. Above 1000 K, the interface conduction is degrading due to a thermal instability. Both stoichiometry variation in as-grown films and thermal instability are attributed to the preferential evaporation of gallium from the NGO thin films at elevated temperatures.

Disentanglement of growth dynamic and thermodynamic effects in LaAlO3/SrTiO3 heterostructures.

The influence of non-equilibrium and equilibrium processes during growth of LaAlO3/SrTiO3 (LAO/STO) heterostructures is analyzed. We investigate the electronic properties of LAO/STO heterostructures obtained at constant growth conditions after annealing in different oxygen atmospheres within the typical growth window (1 × 10−4 mbar –1 × 10−2 mbar). The variation of annealing conditions is found to cause a similar change of electronic properties as observed for samples grown in different oxygen pressure. The results indicate that equilibrium defect formation is the dominant process for establishing the properties of the two-dimensional electron gas (2DEG), while growth dynamics play a minor role in the typical LAO/STO growth regime. Furthermore, the effects of non-equilibrium processes occurring during growth are investigated in detail by quenching just-grown LAO/STO heterostructures directly after growth. We show that during growth the sample is pushed into a non-equilibrium state. After growth, the sample then relaxes towards equilibrium, while the relaxation rate strongly depends on the ambient pressure. The observed relaxation behavior is mainly associated with a reoxidation of the STO bulk, while the 2DEG is formed immediately after the growth.

Surface Termination Conversion during SrTiO3 Thin Film Growth Revealed by X-ray Photoelectron Spectroscopy.

Emerging electrical and magnetic properties of oxide interfaces are often dominated by the termination and stoichiometry of substrates and thin films, which depend critically on the growth conditions. Currently, these quantities have to be measured separately with different sophisticated techniques. This report will demonstrate that the analysis of angle dependent X-ray photoelectron intensity ratios provides a unique tool to determine both termination and stoichiometry simultaneously in a straightforward experiment. Fitting the experimental angle dependence with a simple analytical model directly yields both values. The model is calibrated through the determination of the termination of SrTiO3 single crystals after systematic pulsed laser deposition of sub-monolayer thin films of SrO. We then use the model to demonstrate that during homoepitaxial SrTiO3 growth, excess Sr cations are consumed in a self-organized surface termination conversion before cation defects are incorporated into the film. We show that this termination conversion results in insulating properties of interfaces between polar perovskites and SrTiO3 thin films. These insights about oxide thin film growth can be utilized for interface engineering of oxide heterostructures. In particular, they suggest a recipe for obtaining two-dimensional electron gases at thin film interfaces: SrTiO3 should be deposited slightly Ti-rich to conserve the TiO2-termination.

Atomic-scale measurement of structure and chemistry of a single-unit-cell layer of LaAlO3 embedded in SrTiO3

A single layer of LaAlO3 with a nominal thickness of one unit cell, which is sandwiched between a SrTiO3 substrate and a SrTiO3 capping layer, is quantitatively investigated by high-resolution transmission electron microscopy. By the use of an aberration-corrected electron microscope and by employing sophisticated numerical image simulation procedures, significant progress is made in two aspects. First, the structural as well as the chemical features of the interface are determined simultaneously on an atomic scale from the same specimen area. Second, the evaluation of the structural and chemical data is carried out in a fully quantitative way on the basis of the absolute image contrast, which has not been achieved so far in materials science investigations using high-resolution electron microscopy. Considering the strong influence of even subtle structural details on the electronic properties of interfaces in oxide materials, a fully quantitative interface analysis, which makes positional data available with picometer precision together with the related chemical information, can contribute to a better understanding of the functionality of such interfaces.

Oxygen partial pressure dependence of surface space charge formation in donor-doped SrTiO3

In this study, we investigated the electronic surface structure of donor-doped strontium titanate. Homoepitaxial 0.5 wt. % donor-doped SrTiO3 thin films were analyzed by in situ near ambient pressure X-ray photoelectron spectroscopy at a temperature of 770 K and oxygen pressures up to 5 mbar. Upon exposure to an oxygen atmosphere at elevated temperatures, we observed a rigid binding energy shift of up to 0.6 eV towards lower binding energies with respect to vacuum conditions for all SrTiO3 core level peaks and the valence band maximum with increasing oxygen pressure. The rigid shift is attributed to a relative shift of the Fermi energy towards the valence band concomitant with a negative charge accumulation at the surface, resulting in a compensating electron depletion layer in the near surface region. Charge trapping effects solely based on carbon contaminants are unlikely due to their irreversible desorption under the given experimental conditions. In addition, simple reoxygenation of oxygen vacancies c...

Pulsed laser deposition of SrRuO3 thin-films: The role of the pulse repetition rate

SrRuO3 thin-films were deposited with different pulse repetition rates, fdep, epitaxially on vicinal SrTiO3 substrates by means of pulsed laser deposition. The measurement of several physical properties (e.g., composition by means of X-ray photoelectron spectroscopy, the out-of-plane lattice parameter, the electric conductivity, and the Curie temperature) consistently reveals that an increase in laser repetition rate results in an increase in ruthenium deficiency in the films. By the same token, it is shown that when using low repetition rates, approaching a nearly stoichiometric cation ratio in SrRuO3 becomes feasible. Based on these results, we propose a mechanism to explain the widely observed Ru deficiency of SrRuO3 thin-films. Our findings demand these theoretical considerations to be based on kinetic rather than widely employed thermodynamic arguments.

Unraveling the enhanced Oxygen Vacancy Formation in Complex Oxides during Annealing and Growth

The reduction of oxides during annealing and growth in low pressure processes is a widely known problem. We hence investigate the influence of mere annealing and of growth in vacuum systems to shed light on the reasons behind the reduction of perovskites. When comparing the existing literature regarding the reduction of the perovskite model material SrTiO3 it is conspicuous that one finds different oxygen pressures required to achieve reduction for vacuum annealing and for chemically controlled reducing atmospheres. The unraveling of this discrepancy is of high interest for low pressure physical vapor depositions of thin films heterostructures to gain further understanding of the reduction of the SrTiO3. For thermal annealing, our results prove the attached measurement devices (mass spectrometer/ cold cathode gauge) to be primarily responsible for the reduction of SrTiO3 in the deposition chamber by shifting the thermodynamic equilibrium to a more reducing atmosphere. We investigated the impact of our findings on the pulsed laser deposition growth at low pressure for LaAlO3/SrTiO3. During deposition the reduction triggered by the presence of the laser plume dominates and the impact of the measurement devices plays a minor role. During post annealing a complete reoxidization of samples is inhibited by an insufficient supply of oxygen.

Mobility Modulation and Suppression of Defect Formation in Two-Dimensional Electron Systems by Charge-Transfer Management

Electron mobility is one of the most-debated key attributes of low-dimensional electron systems emerging at complex oxide heterointerfaces. However, a common understanding of how electron mobility can be optimized in these systems has not been achieved so far. Here, we discuss a novel approach for achieving a systematic increase in electron mobility in polar/nonpolar perovskite interfaces by suppressing the thermodynamically required defect formation at the nanoscale. We discuss the transport properties of electron gases established at interfaces between SrTiO3 and various polar perovskites [LaAlO3, NdGaO3, and (La,Sr)(Al,Ta)O3], allowing for the individual variation of epitaxial strain and charge transfer among these epitaxial interfaces. As we show, the reduced charge transfer at (La,Sr)(Al,Ta)O3/SrTiO3 interfaces yields a systematic increase in electron mobility, while the reduced epitaxial strain has only minor impact. As thermodynamic continuum simulations suggest, the charge transfer across these interfaces affects both the spatial distribution of electrons and the background distribution of ionic defects, acting as major scatter centers within the potential well. Easing charge transfer in (La,Sr)(Al,Ta)O3/SrTiO3 yields an enlarged spatial separation of mobile charge carriers and scattering centers, as well as a reduced driving force for the formation of ionic defects at the nanoscale. Our results suggest a general recipe for achieving electron enhancements at oxide heterostructure interfaces and provide new perspectives for atomistic understanding of electron scattering in these systems.