In many transition metal oxides, 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 use a model homoepitaxial system of SrTiO3 (STO) thin films on single crystal STO substrates. Physical property measurements indicate that oxygen vacancy generation in high vacuum is strongly influenced by the energetics of the laser plume, and it can be controlled by proper laser beam delivery. Therefore, our finding not only provides essential insight into oxygen stoichiometry control in high vacuum for understanding the fundamental properties of STO-based thin films and heterostructures, but expands the utility of pulsed laser epitaxy of other materials as well.

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Growth control of oxygen stoichiometry in homoepitaxial SrTiO3 films by pulsed laser epitaxy in high vacuum

Inferior charge transport in insulating and bulk discharge products is one of the main factors resulting in poor cycling stability of lithium-oxygen batteries with high overpotential and large capacity decay. Here we report a two-step oxygen reduction approach by pre-depositing a potassium carbonate layer on the cathode surface in a potassium-oxygen battery to direct the growth of defective film-like discharge products in the successive cycling of lithium-oxygen batteries. The formation of defective film with improved charge transport and large contact area with a catalyst plays a critical role in the facile decomposition of discharge products and the sustained stability of the battery. Multistaged discharge constructing lithium peroxide-based heterostructure with band discontinuities and a relatively low lithium diffusion barrier may be responsible for the growth of defective film-like discharge products. This strategy offers a promising route for future development of cathode catalysts that can be used to extend the cycling life of lithium-oxygen batteries.

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Multistaged discharge constructing heterostructure with enhanced solid-solution behavior for long-life lithium-oxygen batteries.

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 use a model homoepitaxial system of SrTiO3 (STO) thin films on single crystal STO substrates. Physical property measurements indicate that oxygen vacancy generation in high vacuum is strongly influenced by the energetics of the laser plume, and it can be controlled by proper laser beam delivery. Therefore, our finding not only provides essential insight into oxygen stoichiometry control in high vacuum for understanding the fundamental properties of STO-based thin films and heterostructures, but expands the utility of pulsed laser epitaxy of other materials as well.

/pdf/growth-control-of-oxygen-stoichiometry-in-homoepitaxial-4jdp29dx8l.pdf

The oxidation of species in the plasma plume during pulsed laser deposition controls both the stoichiometry as well as the growth kinetics of the deposited SrTiO3 thin films, instead of the commonly assumed mass distribution in the plasma plume and the kinetic energy of the arriving species. It was observed by X-ray diffraction that SrTiO3 stoichiometry depends on the composition of the background gas during deposition, where in a relative small pressure range between 10−2 mbars and 10−1 mbars oxygen partial pressure, the resulting film becomes fully stoichiometric. Furthermore, upon increasing the oxygen (partial) pressure, the growth mode changes from 3D island growth to a 2D layer-by-layer growth mode as observed by reflection high energy electron diffraction.

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Research Update: Stoichiometry controlled oxide thin film growth by pulsed laser deposition

Obtaining high-quality thin films of 5d transition metal oxides is essential to explore the exotic semimetallic and topological phases predicted to arise from the combination of strong electron correlations and spin-orbit coupling. Here, we show that the transport properties of SrIrO3 thin films, grown by pulsed laser deposition, can be optimized by considering the effect of laser-induced modification of the SrIrO3 target surface. We further demonstrate that bare SrIrO3 thin films are subject to degradation in air and are highly sensitive to lithographic processing. A crystalline SrTiO3 cap layer deposited in-situ is effective in preserving the film quality, allowing us to measure metallic transport behavior in films with thicknesses down to 4 unit cells. In addition, the SrTiO3 encapsulation enables the fabrication of devices such as Hall bars without altering the film properties, allowing precise (magneto)transport measurements on micro- and nanoscale devices.

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Epitaxial growth and thermodynamic stability of SrIrO 3 /SrTiO 3 heterostructures

We studied the pulsed laser deposition of homoepitaxial SrTiO3 thin films in different deposition regimes in order to elucidate the possibility to promote two-dimensional growth by increasing the kinetic energy of the oncoming particles. The kinetic energy of the oncoming species is determined by exploiting plume diagnostics techniques and the resulting nucleation and growth processes are analysed by reflection high-energy electron diffraction and atomic force microscopy. We could show that although the kinetic energy of the oncoming species varies to a great extent, the diffusion process is mostly influenced by the stoichiometry. Under stoichiometric conditions, obtained only in a limited window of process parameters, the adatoms on the surface have the highest diffusivity, thus promoting a step-flow growth mode. Under nonstoichiometric conditions, both Sr- and Ti-rich, the diffusivity is strongly reduced. This results in a transition from a two-dimensional to a three-dimensional growth under Sr-rich conditions. Conversely, in the Ti-rich case, obtained at high laser fluence, the two-dimensional growth sustains until the end of the growth process. We attribute this to the high island density available at high laser fluence which facilitates the diffusion of adatoms to step edges despite of their reduced diffusion length.

https://iopscience.iop.org/article/10.1088/0022-3727/47/3/034009/pdf

A Sambri

Papers

Impact of the interplay between nonstoichiometry and kinetic energy of the plume species on the growth mode of SrTiO 3 thin films