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Finding high-voltage Ca cathode materials is a critical step to unleashing the full potential of high-energy-density Ca-ion batteries. First-principles calculations are used to demonstrate that P-type layered calcium transition metal (TM) oxide materials (CaTM2O4) with a range of TM substitutions (TM = Ti, V, Cr, Mn, Fe, Co, and Ni) have excellent battery-related properties including thermodynamic stability, average voltage, energy density, synthesizability, ionic mobility, and electronic structure. However, the thermodynamic stability of the charged phase and TM redox activity are shown to be sensitive to TM selection, with CaCo2O4 having the best balance of all considered properties. The utility of combining multiple TMs to expand the chemical search space for TM substitutions is demonstrated by mixing Co and Ni in layered CaTM2O4.

High purity niobium (Nb), subjected to the processing methods used in the fabrication of superconducting RF cavities, displays micron-sized surface patches containing excess carbon. High-resolution transmission electron microscopy and electron energy-loss spectroscopy measurements are presented which reveal the presence of nanoscale NbC coherent precipitates in such regions. Raman backscatter spectroscopy on similar surface regions exhibit spectra consistent with the literature results on bulk NbC but with significantly enhanced two-phonon scattering. The unprecedented strength and sharpness of the two-phonon signal has prompted a theoretical analysis, using density functional theory (DFT), of phonon modes in NbC for two different interface models of the coherent precipitate. One model leads to overall compressive strain and a comparison to ab-initio calculations of phonon dispersion curves under uniform compression of the NbC shows that the measured two-phonon peaks are linked directly to phonon anomalies arising from strong electron-phonon interaction. Another model of the extended interface between Nb and NbC, studied by DFT, gives insight into the frequency shifts of the acoustic and optical mode density of states measured by first order Raman. The exact origin of the stronger two-phonon response is not known at present but it suggests the possibility of enhanced electron-phonon coupling in transition metal carbides under strain found either in the bulk NbC inclusions or at their interfaces with Nb metal. Preliminary tunneling studies using a point contact method show some energy gaps larger than expected for bulk NbC., The authors thank G. Ciovati of Jefferson Laboratory for supplying Nb samples used in this study. Calculations (H.L.) were performed with financial support by the SSF-project Designed multicomponent coatings, MultiFilms and the Swedish Research Council. Calculations were carried out at the Swedish National Infrastructure for Computing (SNIC), Argonne LCRC and Argonne Center for Nanoscale Materials. The work at Argonne National Laboratory and the use of the Center for Nanoscale Materials and the Electron Microscopy center at Argonne National Laboratory were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-06CH11357. This work was also supported by the Department of Energy, Office of Science, Office of High Energy Physics, early career award FWP#50335 to T.P.

High purity niobium (Nb), subjected to the processing methods used in the fabrication of superconducting RF cavities, displays micron-sized surface patches containing excess carbon. High-resolution transmission electron microscopy and electron energy-loss spectroscopy measurements are presented which reveal the presence of nanoscale NbC coherent precipitates in such regions. Raman backscatter spectroscopy on similar surface regions exhibit spectra consistent with the literature results on bulk NbC but with significantly enhanced two-phonon scattering. The unprecedented strength and sharpness of the two-phonon signal has prompted a theoretical analysis, using density functional theory (DFT), of phonon modes in NbC for two different interface models of the coherent precipitate. One model leads to overall compressive strain and a comparison to ab-initio calculations of phonon dispersion curves under uniform compression of the NbC shows that the measured two-phonon peaks are linked directly to phonon anomalies arising from strong electron-phonon interaction. Another model of the extended interface between Nb and NbC, studied by DFT, gives insight into the frequency shifts of the acoustic and optical mode density of states measured by first order Raman. The exact origin of the stronger two-phonon response is not known at present but it suggests the possibility of enhanced electron-phonon coupling in transition metal carbides under strain found either in the bulk NbC inclusions or at their interfaces with Nb metal. Preliminary tunneling studies using a point contact method show some energy gaps larger than expected for bulk NbC., The authors thank G. Ciovati of Jefferson Laboratory for supplying Nb samples used in this study. Calculations (H.L.) were performed with financial support by the SSF-project Designed multicomponent coatings, MultiFilms and the Swedish Research Council. Calculations were carried out at the Swedish National Infrastructure for Computing (SNIC), Argonne LCRC and Argonne Center for Nanoscale Materials. The work at Argonne National Laboratory and the use of the Center for Nanoscale Materials and the Electron Microscopy center at Argonne National Laboratory were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-06CH11357. This work was also supported by the Department of Energy, Office of Science, Office of High Energy Physics, early career award FWP#50335 to T.P.

Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surface layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. Our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments.

Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surface layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. Our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments.

Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surface layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. Our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments.

High purity niobium (Nb), subjected to the processing methods used in the fabrication of superconducting RF cavities, displays micron-sized surface patches containing excess carbon. High-resolution transmission electron microscopy and electron energy-loss spectroscopy measurements are presented which reveal the presence of nanoscale NbC coherent precipitates in such regions. Raman backscatter spectroscopy on similar surface regions exhibit spectra consistent with the literature results on bulk NbC but with significantly enhanced two-phonon scattering. The unprecedented strength and sharpness of the two-phonon signal has prompted a theoretical analysis, using density functional theory (DFT), of phonon modes in NbC for two different interface models of the coherent precipitate. One model leads to overall compressive strain and a comparison to ab-initio calculations of phonon dispersion curves under uniform compression of the NbC shows that the measured two-phonon peaks are linked directly to phonon anomalies arising from strong electron-phonon interaction. Another model of the extended interface between Nb and NbC, studied by DFT, gives insight into the frequency shifts of the acoustic and optical mode density of states measured by first order Raman. The exact origin of the stronger two-phonon response is not known at present but it suggests the possibility of enhanced electron-phonon coupling in transition metal carbides under strain found either in the bulk NbC inclusions or at their interfaces with Nb metal. Preliminary tunneling studies using a point contact method show some energy gaps larger than expected for bulk NbC., The authors thank G. Ciovati of Jefferson Laboratory for supplying Nb samples used in this study. Calculations (H.L.) were performed with financial support by the SSF-project Designed multicomponent coatings, MultiFilms and the Swedish Research Council. Calculations were carried out at the Swedish National Infrastructure for Computing (SNIC), Argonne LCRC and Argonne Center for Nanoscale Materials. The work at Argonne National Laboratory and the use of the Center for Nanoscale Materials and the Electron Microscopy center at Argonne National Laboratory were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-06CH11357. This work was also supported by the Department of Energy, Office of Science, Office of High Energy Physics, early career award FWP#50335 to T.P.

High purity niobium (Nb), subjected to the processing methods used in the fabrication of superconducting RF cavities, displays micron-sized surface patches containing excess carbon. High-resolution transmission electron microscopy and electron energy-loss spectroscopy measurements are presented which reveal the presence of nanoscale NbC coherent precipitates in such regions. Raman backscatter spectroscopy on similar surface regions exhibit spectra consistent with the literature results on bulk NbC but with significantly enhanced two-phonon scattering. The unprecedented strength and sharpness of the two-phonon signal has prompted a theoretical analysis, using density functional theory (DFT), of phonon modes in NbC for two different interface models of the coherent precipitate. One model leads to overall compressive strain and a comparison to ab-initio calculations of phonon dispersion curves under uniform compression of the NbC shows that the measured two-phonon peaks are linked directly to phonon anomalies arising from strong electron-phonon interaction. Another model of the extended interface between Nb and NbC, studied by DFT, gives insight into the frequency shifts of the acoustic and optical mode density of states measured by first order Raman. The exact origin of the stronger two-phonon response is not known at present but it suggests the possibility of enhanced electron-phonon coupling in transition metal carbides under strain found either in the bulk NbC inclusions or at their interfaces with Nb metal. Preliminary tunneling studies using a point contact method show some energy gaps larger than expected for bulk NbC., The authors thank G. Ciovati of Jefferson Laboratory for supplying Nb samples used in this study. Calculations (H.L.) were performed with financial support by the SSF-project Designed multicomponent coatings, MultiFilms and the Swedish Research Council. Calculations were carried out at the Swedish National Infrastructure for Computing (SNIC), Argonne LCRC and Argonne Center for Nanoscale Materials. The work at Argonne National Laboratory and the use of the Center for Nanoscale Materials and the Electron Microscopy center at Argonne National Laboratory were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-06CH11357. This work was also supported by the Department of Energy, Office of Science, Office of High Energy Physics, early career award FWP#50335 to T.P.

High purity niobium (Nb), subjected to the processing methods used in the fabrication of superconducting RF cavities, displays micron-sized surface patches containing excess carbon. High-resolution transmission electron microscopy and electron energy-loss spectroscopy measurements are presented which reveal the presence of nanoscale NbC coherent precipitates in such regions. Raman backscatter spectroscopy on similar surface regions exhibit spectra consistent with the literature results on bulk NbC but with significantly enhanced two-phonon scattering. The unprecedented strength and sharpness of the two-phonon signal has prompted a theoretical analysis, using density functional theory (DFT), of phonon modes in NbC for two different interface models of the coherent precipitate. One model leads to overall compressive strain and a comparison to ab-initio calculations of phonon dispersion curves under uniform compression of the NbC shows that the measured two-phonon peaks are linked directly to phonon anomalies arising from strong electron-phonon interaction. Another model of the extended interface between Nb and NbC, studied by DFT, gives insight into the frequency shifts of the acoustic and optical mode density of states measured by first order Raman. The exact origin of the stronger two-phonon response is not known at present but it suggests the possibility of enhanced electron-phonon coupling in transition metal carbides under strain found either in the bulk NbC inclusions or at their interfaces with Nb metal. Preliminary tunneling studies using a point contact method show some energy gaps larger than expected for bulk NbC., The authors thank G. Ciovati of Jefferson Laboratory for supplying Nb samples used in this study. Calculations (H.L.) were performed with financial support by the SSF-project Designed multicomponent coatings, MultiFilms and the Swedish Research Council. Calculations were carried out at the Swedish National Infrastructure for Computing (SNIC), Argonne LCRC and Argonne Center for Nanoscale Materials. The work at Argonne National Laboratory and the use of the Center for Nanoscale Materials and the Electron Microscopy center at Argonne National Laboratory were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-06CH11357. This work was also supported by the Department of Energy, Office of Science, Office of High Energy Physics, early career award FWP#50335 to T.P.

Using in situ grazing-incidence x-ray scattering, we have measured the diffuse scattering from islands that form during layer-by-layer growth of GaN by metal-organic vapor phase epitaxy on the (101⎯⎯0)(101¯0)(101¯0) m-plane surface. The diffuse scattering is extended in the (0001)(0001)(0001) in-plane direction in reciprocal space, indicating a strong anisotropy with islands elongated along [12⎯⎯10][12¯10] [12¯10] and closely spaced along [0001][0001][0001]. This is confirmed by atomic force microscopy of a quenched sample. Islands were characterized as a function of growth rate F and temperature. The island spacing along [0001][0001][0001] observed during the growth of the first monolayer obeys a power-law dependence on growth rate F−nF−nF−n, with an exponent n=0.25±0.02n=0.25±0.02n=0.25±0.02. The results are in agreement with recent kinetic Monte Carlo simulations, indicating that elongated islands result from the dominant anisotropy in step edge energy and not from surface diffusion anisotropy. The observed power-law exponent can be explained using a simple steady-state model, which gives n = 1/4.