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Epitaxial growth is a powerful tool for synthesizing heterostructures and integrating multiple functionalities. However, interfacial mixing can readily occur and significantly modify the properties of layered structures, particularly for those containing energy storage materials with smaller cations. Here, we show a two-step sequence involving the growth of an epitaxial LiCoO

The functionality of magnetite, Fe3O4, for catalysis and spintronics applications is dependent on the molar ratio of Fe2+ and Fe3+ and their distribution at the surface. In turn, this depends on a poorly understood interplay between crystallographic orientation, dopants, and the reactive adsorption of atmospheric species such as water. Here, (100)-, (110)-, and (111)-oriented films of titanomagnetite, Fe(3-x)TixO4, were grown by pulsed laser deposition and their composition, valence distribution, magnetism, and interaction with water were studied by ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and X-ray magnetic circular dichroism. Although the bulk compositions match the desired stoichiometry, the surfaces were found to be enriched in Ti4+, especially the top 1 nm. The highest surface energy (110) film was the most reduced, tied to local Ti enrichment, and a corresponding decreased magnetic moment. AP-XPS showed that incorporation of x = 0.25 Ti dramatically lowered the propensity to form hydroxyl species at a given relative humidity, and also that hydroxylation is relatively invariant with orientation. In contrast, the affinity for water is similar across orientations, regardless of Ti incorporation, suggesting that relative humidity controls its uptake. The findings may help demystify the interactions that lead to specific distributions of Fe2+ and Fe3+ at magnetite surfaces, toward design of more deliberately active catalysts and magnetic devices.

We assess the validity of criteria based on size mismatch and thermodynamics in predicting the stability of the rare class of high-entropy alloys (HEAs) that form in the hexagonal close-packed crystal structure. We focus on nanocrystalline HEA particles composed predominantly of Mo, Tc, Ru, Rh, and Pd along with Ag, Cd, and Te, which are produced in uranium dioxide fuel under the extreme conditions of nuclear reactor operation. The constituent elements are fission products that aggregate under the combined effects of irradiation and elevated temperature as high as 1200 °C. We present the recent results on alloy nanoparticle formation in irradiated ceria, which was selected as a surrogate for uranium dioxide, to show that radiation-enhanced diffusion plays an important role in the process. This work sheds light on the initial stages of alloy nanoparticle formation from a uniform dispersion of individual metals. The remarkable chemical durability of such multiple principal element alloys presents a solution, namely, an alloy waste form, to the challenge of immobilizing Tc.

Metallic particles formed in oxide fuels (e.g., UO2) during neutron irradiation have an adverse impact on fuel performance. A fundamental investigation of particle precipitation is needed to predict the fuel performance and potentially improve fuel designs and operations. This study reports on the precipitation of Mo-dominant β-phase particles in polycrystalline CeO2 (surrogate for UO2) films doped with Mo, Pd, Rh, Ru, and Re (surrogate for Tc). In situ heating scanning transmission electron microscopy indicates that particle precipitation starts at ∼1073 K with a limited particle growth to ∼10 nm. While particle concentration increases with increasing temperature, particle size remains largely unchanged up to 1273 K. There is a dramatic change in the microstructure following vacuum annealing at 1373 K, probably due to phase transition of reduced cerium oxide. At the high temperature, particles grow up to 75 nm or larger with distinctive facets. The particles are predominantly composed of Mo with a body-c...

Epsilon-phase alloy precipitates have been observed with varied compositions and sizes in spent nuclear fuels, such as UO2. The presence of the inclusions, along with other oxide precipitates, gas bubbles, and irradiation-induced structural defects, can significantly degrade the physical properties of the fuel. To predict fuel performance, a fundamental study of the precipitation processes is needed. This study uses ceria (CeO2) as a surrogate for UO2. Polycrystalline CeO2 films doped with Mo, Ru, Rh, Pd, and Re (surrogate for Tc) were grown at 823 K using pulsed laser deposition, irradiated at 673 K with He+ ions, and subsequently annealed at higher temperatures. A number of methods, including transmission electron microscopy and atom probe tomography, were applied to characterize the samples. The results indicate that there is a uniform distribution of the doped metals in the as-grown CeO2 film. Pd particles of ∼3 nm in size appear near the dislocation edges after He+ ion irradiation to ∼13 dpa. Thermal...

Understanding the interaction of water with compositionally tuned metal oxides is central to exploiting their unique catalytic and magnetic properties. However, processes such as hydroxylation, wetting, and resulting changes in electronic structure at ambient conditions are challenging to probe in situ. Here, we examine the hydroxylation and wetting of Fe(3–x)TixO4 (001)-oriented epitaxial films directly using ambient pressure X-ray photoelectron spectroscopy under controlled relative humidity. Fe2+ formation promoted by Ti4+ substitution for Fe3+ increases with hydroxylation, commensurate with a decrease in the surface work function or change in the surface dipole. The incorporation of small amounts of Ti (x = 0.25) as a bulk dopant dramatically impacts hydroxylation, in part due to surface segregation, leading to coverages closer to that of TiO2 than Fe3O4. However, the Fe(3–x)TixO4 compositional series shows a similar affinity for water physisorption, which begins at notably lower relative humidity tha...

Polarization-induced weak ferromagnetism (WFM) was demonstrated a few years back in LiNbO3-type compounds, MTiO3 (M = Fe, Mn, Ni). Although the coexistence of ferroelectric polarization and ferromagnetism has been demonstrated in this rare multiferroic family before, first in bulk FeTiO3, then in thin-film NiTiO3, the coupling of the two order parameters has not been confirmed. Here, we report the stabilization of polar, ferromagnetic NiTiO3 by oxide epitaxy on a LiNbO3 substrate utilizing tensile strain and demonstrate the theoretically predicted coupling between its polarization and ferromagnetism by X-ray magnetic circular dichroism under applied fields. The experimentally observed direction of ferroic ordering in the film is supported by simulations using the phase-field approach. Our work validates symmetry-based criteria and first-principles calculations of the coexistence of ferroelectricity and WFM in MTiO3 transition metal titanates crystallizing in the LiNbO3 structure. It also demonstrates the ...

Complex oxides and semiconductors exhibit distinct yet complementary properties owing to their respective ionic and covalent natures. By electrically coupling complex oxides to traditional semiconductors within epitaxial heterostructures, enhanced or novel functionalities beyond those of the constituent materials can potentially be realized. Essential to electrically coupling complex oxides to semiconductors is control of the physical structure of the epitaxially grown oxide, as well as the electronic structure of the interface. Here we discuss how composition of the perovskite A- and B-site cations can be manipulated to control the physical and electronic structure of semiconductor—complex oxide heterostructures. Two prototypical heterostructures, Ba1−xSrxTiO3/Ge and SrZrxTi1−xO3/Ge, will be discussed. In the case of Ba1−xSrxTiO3/Ge, we discuss how strain can be engineered through A-site composition to enable the re-orientable ferroelectric polarization of the former to be coupled to carriers in the semiconductor. In the case of SrZrxTi1−xO3/Ge we discuss how B-site composition can be exploited to control the band offset at the interface. Analogous to heterojunctions between compound semiconducting materials, control of band offsets, i.e., band-gap engineering, provides a pathway to electrically couple complex oxides to semiconductors to realize a host of functionalities.

Double perovskites of the form R2BB′O6 (where R is a rare earth cation and B and B′ are chemically distinct transition metal cations with half-filled and empty eg orbitals, respectively) are of significant interest for their magnetoelectric properties. La2MnNiO6 is particularly attractive because of its large expected ferromagnetic moment per formula unit (5 μB f.u.–1) and its semiconducting character. If the ideal structure nucleates, superexchange coupling can take place via the B—O—B′ bonds that form, and the moment per formula unit can attain its maximum theoretical value. However, we show that even in the case of layer-by-layer deposition via molecular beam epitaxy, the system can follow multiple reaction pathways that lead to deviations from the double perovskite structure. In particular, we observe a spatially extended phase in which B-site cation disorder occurs, resulting in Mn—O—Mn and Ni—O—Ni antiferromagnetic domains, as well as the formation of quasi-epitaxial, antiferromagnetic NiO nanoscale...

Pacific Northwest National Laboratory (PNNL), in collaboration with government agencies and industries, is actively engaged in the development, testing, and characterization of high efficiency, low cost modular solid oxide fuel cell power generation systems for stationary, automotive and military applications. Advanced SOFC systems are being developed which will offer ease of operation on a variety of gaseous liquid hydrocarbon and coal-derived fuels as well as "zero emissions" capability. SOFC R&D activities at PNNL continue in the areas of cell component materials, electrochemistry, cell design and modeling, high temperature corrosion, and fuel processing. Specific activities include development of optimized materials and cost effective fabrication techniques for high power density anode-supported cells operating at temperatures below 800 degrees C, characterization of processes responsible for high electrical performance and long term performance degradation, optimization and cell and stack designs using computational engineering models, and hydrocarbon fuel processing using micro technology.

Nonuniform and highly localized Li dendrites are known to cause deleterious and, in many cases, catastrophic effects on the performance of rechargeable Li batteries. However, the mechanisms of cathode failures upon contact with Li metal are far from clear. In this study, using in situ transmission electron microscopy, the interaction of Li metal with well-defined, epitaxial thin films of LiCoO

Identification of kinetic and thermodynamic factors that control crystal nucleation and growth represents a central challenge in materials synthesis. Here we report that apparently defect-free growth of ${\mathrm{La}}_{2}{\mathrm{MnNiO}}_{6}$ (LMNO) thin films supported on ${\mathrm{SrTiO}}_{3}$ (STO) proceeds up to 1--5 nm, after which it is disrupted by precipitation of NiO phases. Local geometric phase analysis and ensemble-averaged x-ray reciprocal space mapping show no change in the film strain away from the interface, indicating that mechanisms other than strain relaxation induce the formation of the NiO phases. Ab initio simulations suggest that the electrostatic potential build-up associated with the polarity mismatch at the film-substrate interface promotes the formation of oxygen vacancies with increasing thickness. In turn, oxygen deficiency promotes the formation of Ni-rich regions, which points to the built-in potential as an additional factor that contributes to the NiO precipitation mechanisms. These results suggest that the precipitate-free region could be extended further by either incorporating dopants that suppress the built-in potential or by increasing the oxygen fugacity in order to suppress the formation of oxygen vacancies.

Complex oxides and semiconductors exhibit distinct yet complementary properties owing to their respective ionic and covalent natures. By electrically coupling oxides to semiconductors within epitaxial heterostructures, enhanced or novel functionalities beyond those of the constituent materials can potentially be realized. Key to electrically coupling oxides to semiconductors is controlling the physical and electronic structure of semiconductor – crystalline oxide heterostructures. Here we discuss how composition of the oxide can be manipulated to control physical and electronic structure in Ba1-xSrxTiO3/ Ge and SrZrxTi1-xO3/Ge heterostructures. In the case of the former we discuss how strain can be engineered through composition to enable the re-orientable ferroelectric polarization to be coupled to carriers in the semiconductor. In the case of the latter we discuss how composition can be exploited to control the band offset at the semiconductor - oxide interface. The ability to control the band offset, i.e. band-gap engineering, provides a pathway to electrically couple crystalline oxides to semiconductors to realize a host of functionalities.

Hysteretic behavior was studied in a series of Fe thin films, grown by molecular beam epitaxy, having different grain sizes and grown on different substrates. Major and minor loops and first order reversal curves (FORCs) were collected to investigate magnetization mechanisms and domain behavior under different magnetic histories. The minor loop coefficient and major loop coercivity increase with decreasing grain size due to higher defect concentration resisting domain wall movement. First order reversal curves allowed estimation of the contribution of irreversible and reversible susceptibilities and switching field distribution. The differences in shape of the major loops and first order reversal curves are described using a classical Preisach model with distributions of hysterons of different switching fields, providing a powerful visualization tool to help understand the magnetization switching behavior of Fe films as manifested in various experimental magnetization measurements.

We show that despite very similar crystallographic properties and work function values in bulk Fe and Cr, epitaxial films of these metals on Nb:SrTiO3(001) exhibit completely different heterojunction electronic properties. The Cr/SrTiO3 interface is ohmic, whereas Fe/SrTiO3 forms a Schottky barrier with a barrier height of 0.50 eV. This difference arises because of variations in interface chemistry. In contrast to Cr [Chambers, S. A. , Adv. Mater. 2013, 25, 4001.], in-diffused Fe exhibits a +2 oxidation state and occupies Ti sites in the perovskite lattice, resulting in negligible charge transfer to Ti, upward band bending, and Schottky barrier formation. The differences between Cr and Fe are understood by performing first-principles calculations of the energetics of defect formation, which corroborate experimental results.

Polarization-induced weak ferromagnetism has been predicted a few years back in compounds MTiO 3 (M = Fe, Mn, Ni) (Fennie, 2008). We set out to stabilize this metastable, distorted perovskite structure by growing NiTiO 3 epitaxially on sapphire Al 2 O 3 (001) substrate, and to control the polar and magnetic properties via strain. Epitaxial Ni 1 − x Ti 1 − y O 3 films of different Ni/Ti ratios and thicknesses were deposited on Al 2 O 3 substrates by pulsed laser deposition at different temperatures, and characterized using several techniques. The effect of film thickness, deposition temperature, and film stoichiometry on lattice strain, film structure, and physical properties was investigated. Our structural data from x-ray diffraction, electron microscopy, and x-ray absorption spectroscopy shows that substrate-induced strain has a marked effect on the structure and crystalline quality of the films. Physical property measurements reveal a dependence of the Neel transition and lattice polarization on strain, and highlight our ability to control the ferroic properties in NiTiO 3 thin films by film stoichiometry and thickness.

High quantum efficiency enhancement is found for hybrid metal-insulator photocathodes consisting of thin films of CsI deposited on Cu(1 0 0), Ag(1 0 0), Au(1 1 1) and Au films irradiated by 266 nm laser pulses. Low work functions (near or below 2 eV) are observed following ultraviolet laser activation. Work functions are reduced by roughly 3 eV from that of clean metal surfaces. We discuss various mechanisms of quantum efficiency enhancement for alkali halide/metal photocathode systems and conclude that the large change in work function, due to Cs accumulation of Cs metal at the metal–alkali halide interface, is the dominant mechanism for quantum efficiency enhancement.

Ultrathin films of barium oxide were grown on Ag(001) and Ag(111) using the evaporation of Ba metal in an O2 atmosphere by molecular beam epitaxy. Ultraviolet photoemission spectroscopy reveals that films consisting of predominantly BaO or BaO2 result in Ag(001) work function reductions of 1.74 eV and 0.64 eV, respectively. On the Ag(001) surface, Ba oxide growth is initiated by two-dimensional nucleation of epitaxial BaO, followed by a transition to three-dimensional dual-phase nucleation of epitaxial BaO and BaO2. Three-dimensional islands of primarily BaO2(111) nucleate epitaxially on the Ag(111) substrate leaving large patches of Ag uncovered. We find no indication of chemical reaction or charge transfer between the films and the Ag substrates. These data suggest that the origin of the observed work function reduction is largely due to a combination of BaO surface relaxation and an electrostatic compressive effect.

Epitaxial rutile-structured single-crystal Mn x Ti 1 − x O 2 − δ films were synthesized on rutile- (110) and -(001) substrates using pulsed laser deposition. The films were characterized by reflection high-energy electron diffraction (RHEED), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and aberration-corrected transmission electron microscopy (ACTEM). Under the present conditions, 400 °C and P O 2 = 20 mTorr, single crystal epitaxial thin films were grown for x = 0.13, where x is the nominal average mole fraction of Mn. In fact, arbitrarily thick films could be grown with near invariant Mn/Ti concentration profiles from the substrate/film interface to the film surface. In contrast, at x = 0.25, Mn became enriched towards the surface and a secondary nano-scale phase formed which appeared to maintain the basic rutile structure but with enhanced z-contrast in the tunnels, or interstitial sites. Ab initio thermodynamic calculations provided quantitative estimates for the destabilizing effect of expanding the β-MnO 2 lattice parameters to those of TiO 2 -rutile, the stabilizing effect of diluting Mn with increasing Ti concentration, and competing reaction pathways for surface oxide formation.

We have measured high-resolution core-level and valence-band x-ray photoemission spectra for single-crystal $\mathrm{T}{\mathrm{i}}_{2}{\mathrm{O}}_{3}$ cleaved anoxically. The Ti(III) spectra for this lattice are considerably more complex than those measured for Ti(IV)-based oxides due to the presence of a single unpaired electron in the conduction band. This open-shell electron configuration leads to ligand-field split and frequently unresolved multiplets. The Ti $2p$ and $3p$ spectra have been calculated using relativistic Dirac-Hartree-Fock (DHF) theory with the sudden approximation for the intensities. Agreement between theory and experiment is excellent for the $3p$ spectrum, and very good for the $2p$ spectrum, the primary deficiency being a pair of features not captured by theory for the latter. The spectral line shapes are driven by final-state effects associated with angular momentum coupling of the unpaired valence electron with the core hole, one- and two-electron ligand-to-metal charge-transfer (shake) processes accompanying core photoionization, and core-hole screening by conduction-band electrons. The first two of these are accurately predicted by DHF theory with a small embedded cluster containing a single Ti cation and six oxygen ligands. The third effect is not predicted using this cluster in which screening of the core hole from electrons associated with more distant atoms is not possible.

The magnetic susceptibility of synthesized magnetite (Fe3O4) microspheres was found to decline after the growth of a metal–organic framework (MOF) shell on the magnetite core. Detailed structural analysis of the core–shell particles using scanning electron microscopy, transmission electron microscopy, atom probe tomography, and57Fe–Mossbauer spectroscopy suggests that the distribution of MOF precursors inside the magnetic core resulted in the oxidation of the iron oxide core.

Polarization-induced weak ferromagnetism (WFM) was demonstrated a few years back in LiNbO

X-ray photoelectron spectroscopy (XPS) is, in principle, based on a particularly simple process. Electrons within a sample absorb photons of a particular energy and then emerge from the solid. The kinetic energy analysis of electrons emitted from the surface yields information on the electronic states of atoms in the surface region. XPS is prominent in its popularity, versatility, and utility compared with many other techniques. The flexibility and efficacy of XPS will be highlighted through several applications. In addition, a look into spectroscopic imaging as well as future trends may add excitement to this seemingly utilitarian technique.

Nonuniform and highly localized Li dendrites are known to cause deleterious and, in many cases, catastrophic effects on the performance of rechargeable Li batteries. However, the mechanisms of cathode failures upon contact with Li metal are far from clear. In this study, using in situ transmission electron microscopy, the interaction of Li metal with well-defined, epitaxial thin films of LiCoO2 , the most widely used cathode material, is directly visualized at an atomic scale. It is shown that a spontaneous and prompt chemical reaction is triggered once Li contact is made, leading to expansion and pulverization of LiCoO2 and ending with the final reaction products of Li2 O and Co metal. A topotactic phase transition is identified close to the reaction front, resulting in the formation of CoO as a metastable intermediate. Dynamic structural and chemical imaging, in combination with ab initio simulations, reveal that a high density of grain and antiphase boundaries is formed at the reaction front, which are critical for enabling the short-range topotactic reactions and long-range Li propagation. The fundamental insights are of general importance in mitigating Li dendrites related issues and guiding the design principle for more robust energy materials.

Epitaxial chromium ferrite (Fe2CrO4), prepared by state-of-the-art oxygen plasma assisted molecular beam epitaxy, is shown to exhibit unusual electronic transport properties driven by the crystallographic structure and composition of the material. Replacing 1/3 of the Fe cations with Cr converts the host ferrimagnet from a metal into a semiconductor by virtue of its fixed valence (3+); Cr substitutes for Fe at B sites in the spinel lattice. By contrast, replacing 2/3 of the Fe cations with Cr results in an insulator. Three candidate conductive paths, all involving electron hopping between Fe2+ and Fe3+, are identified in Fe2CrO4. Moreover, Fe2CrO4 is shown to be photoconductive across the visible portion of the electromagnetic spectrum. As a result, this material is of potential interest for important photo-electrochemical processes such as water splitting.

Two-dimensional (2D) ultra-high carrier densities at complex oxide interfaces are of considerable current research interest for novel plasmonic and high charge-gain devices. However, the highest 2D electron density obtained in oxide heterostructures is thus far limited to 3×1014 cm-2 (½ electron/unit cell/interface) at GdTiO3/SrTiO3 interfaces, and is typically an order of magnitude lower at LaAlO3/SrTiO3 interfaces. Here we show that carrier densities much higher than 3×1014 cm-2 can be achieved via band engineering. Transport measurements for 3 nm SrTiO3/t u.c. NdTiO3/3 nm SrTiO3/LSAT (001) show that charge transfer significantly in excess of the value expected from the polar discontinuity model occurs for higher t values. The carrier density remains unchanged, and equivalent to ½ electron/unit cell/interface for t < 6 unit cells. However, above a critical NdTiO3 thickness of 6 u.c., electrons from the valence band of NdTiO3 spill over into the SrTiO3 conduction band as a natural consequence of the band alignment. An atomistic model consistent with first-principle calculations and experimental results is proposed for the charge transfer mechanisms. These results may provide an exceptional route to the realization of the room-temperature oxide electronics.