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.
Pulsed Laser Deposition is a commonly used non-equilibrium physical deposition technique for the growth of complex oxide thin films. A wide range of parameters is known to influence the properties of the used samples and thin films, especially the oxygen-vacancy concentration. One parameter has up to this point been neglected due to the challenges of separating its influence from the influence of the impinging species during growth: the UV-radiation of the plasma plume. We here present experiments enabled by a specially designed holder to allow a separation of these two influences. The influence of the UV-irradiation during pulsed laser deposition on the formation of oxygen-vacancies is investigated for the perovskite model material SrTiO3. The carrier concentration of UV-irradiated samples is nearly constant with depth and time. By contrast samples not exposed to the radiation of the plume show a depth dependence and a decrease in concentration over time. We reveal an increase in Ti-vacancy–oxygen-vacancy-complexes for UV irradiated samples, consistent with the different carrier concentrations. We find a UV enhanced oxygen-vacancy incorporation rate as responsible mechanism. We provide a complete picture of another influence parameter to be considered during pulsed laser depositions and unravel the mechanism behind persistent-photo-conductivity in SrTiO3.
a b s t r a c tWe have studied the bonding and elastic properties of amorphous AlYB 14 using theoretical and experimental means. Based on pair distribution functions and Voronoi tessellation, the icosahedral bonding is expected. A rather large Young's modulus of 365 GPa is predicted for amorphous AlYB 14 .To verify these predictions, we have measured density, pair distribution functions, binding energy and elastic properties of Al-Y-B thin films synthesized by magnetron sputtering. The calculated and measured densities are with a deviation of 3.5% in good agreement. The measured binding energy and pair distribution functions are also consistent with icosahedral bonding. The measured Young's modulus is 305 719 GPa, which is 16% smaller than the theoretical value and hence in good agreement. Overall consistency between theory and experiments was obtained indicating that the computational strategy employed here is useful to describe correlations between bonding, elasticity, density as well as (chemical) short range order and may hence enable future knowledge-based design of these ternary borides which show great potential for surface protection applications.
Point defects such as oxygen vacancies cause emergent phenomena such as resistive switching in transition-metal oxides, but their influence on the electron-transport properties is far from being understood. Here, we employ direct mapping of the electronic structure of a memristive device by spectromicroscopy. We find that oxygen vacancies result in in-gap states that we use as input for single-band transport simulations. Because the in-gap states are situated below the Fermi level, they do not contribute to the current directly but impact the shape of the conduction band. Accordingly, we can describe our devices with band-like transport and tunneling across the Schottky barrier at the interface.
This paper introduces a growth method—suboxide molecular-beam epitaxy (S-MBE)—which enables a drastic enhancement in the growth rates of Ga2O3 and related materials to over 1 μm h−1 in an adsorption-controlled regime, combined with excellent crystallinity. Using a Ga + Ga2O3 mixture with an oxygen mole fraction of x(O) = 0.4 as an MBE source, we overcome kinetic limits that had previously hampered the adsorption-controlled growth of Ga2O3 by MBE. We present growth rates up to 1.6 μm h−1 and 1.5 μm h−1 for Ga2O3/Al2O3 and Ga2O3/Ga2O3 structures, respectively, with very high crystalline quality at unparalleled low growth temperature for this level of perfection. We combine thermodynamic knowledge of how to create molecular beams of targeted suboxides with a kinetic model developed for the S-MBE of III–VI compounds to identify appropriate growth conditions. Using S-MBE, we demonstrate the growth of phase-pure, smooth, and high-purity homoepitaxial Ga2O3 films that are thicker than 4.5 μm. With the high growth rate of S-MBE, we anticipate a significant improvement to vertical Ga2O3-based devices. We describe and demonstrate how this growth method can be applied to a wide range of oxides. With respect to growth rates and crystalline quality, S-MBE rivals leading synthesis methods currently used for the production of Ga2O3-based devices.
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