Probing Grain-Boundary Chemistry and Electronic Structure in Proton-Conducting Oxides by Atom Probe Tomography.

A laser-assisted atom-probe-tomographic (LAAPT) method has been developed and applied to measure and characterize the three-dimensional atomic and electronic nanostructure at an yttrium-doped barium zirconate (BaZr0.9Y0.1O3-δ, BZY10) grain boundary. Proton-conducting perovskites, such as BZY10, are attracting intense interest for a variety of energy conversion applications. However, their implementation has been hindered, in part, because of high grain-boundary (GB) resistance that is attributed to a positive GB space-charge layer (SCL). In this study, LAAPT is used to analyze BZY10 GB chemistry in three dimensions with subnanometer resolution. From this analysis, maps of the charge density and electrostatic potential arising at the GBs are derived, revealing for the first time direct chemical evidence that a positive SCL indeed exists at these GBs. These maps reveal new insights on the inhomogeneity of the SCL region and produce an average GB potential barrier of approximately 580 mV, agreeing with previous indirect electrochemical measurements.

Nanoparticles at Grain Boundaries Inhibit the Phase Transformation of Perovskite Membrane.

The high-energy nature of grain boundaries makes them a common source of undesirable phase transformations in polycrystalline materials. In both metals and ceramics, such grain-boundary-induced phase transformation can be a frequent cause of performance degradation. Here, we identify a new stabilization mechanism that involves inhibiting phase transformations of perovskite materials by deliberately introducing nanoparticles at the grain boundaries. The nanoparticles act as "roadblocks" that limit the diffusion of metal ions along the grain boundaries and inhibit heterogeneous nucleation and new phase formation. Ba0.5Sr0.5Co0.8Fe0.2O3-δ, a high-performance oxygen permeation and fuel cell cathode material whose commercial application has so far been impeded by phase instability, is used as an example to illustrate the inhibition action of nanoparticles toward the phase transformation. We obtain stable oxygen permeation flux at 600 °C with an unprecedented 10-1000 times increase in performance compared to previous investigations. This grain boundary stabilization method could potentially be extended to other systems that suffer from performance degradation due to a grain-boundary-initiated heterogeneous nucleation phase transformations.

Solution synthesis and characterization of indium-zinc formate precursors for transparent conducting oxides.

A series of In-Zn formate mixtures were investigated as potential precursors to amorphous In-Zn-oxide (IZO) for transparent conducting oxide (TCO) applications. These mixtures were prepared by neutralization from formic acid and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, and thermogravimetry-differential scanning calorimetry (TG-DSC) measurements. Thermal analysis revealed that a mixture of In and Zn formates reduced the overall decomposition temperature compared to the individual constituents and that OH-substitution enhanced the effect. In terms of precursor feasibility, it was demonstrated that the decomposition products of In-Zn formate could be directed toward oxidation or reduction by controlling the decomposition atmosphere or with solution acid additives. For TCO applications, amorphous IZO films were prepared by ultrasonic spray deposition from In-Zn formate solutions with annealing at 300-400 degrees C.

The Role of Nanoscale Seed Layers on the Enhanced Performance of Niobium doped TiO2 Thin Films on Glass.

Transparent conducting oxide (TCO) coatings with decreased cost and greater process or performance versatility are needed for a variety of optoelectronic applications. Among potential new TCO candidates, doped titanium dioxide is receiving particular interest. In this study, niobium-doped titania bilayer structures consisting of a nanoscale seed layer (deposited by atomic layer deposition or RF magnetron sputtering) followed by a thick bulk-like layer were grown directly on glass in order to examine the effects of the seed layer processing on the subsequent crystallization and electrical properties of these heterostructures. Observations from Raman spectroscopy suggest that higher oxygen content in the seed layer suppresses the formation of detrimental titania polymorph phases, found in films produced by annealing directly after synthesis without any exposure to oxygen. Furthermore, our results indicate that the generation of excellent Nb:TiO2 conductors on glass (without breaking vacuum) only occurs within a narrow processing range and that the sequential deposition of oxygen-poor layers on oxygen-rich layers is a critical step towards achieving films with low resistivity.

Intrinsic Material Properties Dictating Oxygen Vacancy Formation Energetics in Metal Oxides.

Oxygen vacancies (V(O)) in oxides are extensively used to manipulate vital material properties. Although methods to predict defect formation energies have advanced significantly, an understanding of the intrinsic material properties that govern defect energetics lags. We use first-principles calculations to study the connection between intrinsic (bulk) material properties and the energy to form a single, charge neutral oxygen vacancy (E(V)). We investigate 45 binary and ternary oxides and find that a simple model which combines (i) the oxide enthalpy of formation (ΔH(f)), (ii) the midgap energy relative to the O 2p band center (E(O 2p) + (1/2)E(g)), and (iii) atomic electronegativities reproduces calculated E(V) within ∼0.2 eV. This result provides both valuable insights into the key properties influencing E(V) and a direct method to predict E(V). We then predict the E(V) of ∼1800 oxides and validate the predictive nature of our approach against direct defect calculations for a subset of 18 randomly selected materials.