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The interface of a La0.7Sr0.3MnO3/SrTiO3 bilayer was modulated by introducing 3 unit cells of Ba1-xSrxTiO3 using Combinatorial Pulsed Laser Deposition. A wide range of chemical compositions was studied within the same sample, with BSTx stoichiometry variable from 0.5 to 1 along Y-axis, while the SrTiO3 overlayer thickness was modified along the X direction [Fig. 1(a)]. We performed high-resolution, laboratory-based angle-resolved XPS studies of the BSTx film surface providing information on the thickness and composition of the surface and sub-surface layers. Based on the attenuation of the La 3d corelevel photoemission signal from the La0.7Sr0.3MnO3 bottom layer, the BST layer is 1.2 nm thick. XPS Ba 3d5/2 core-level spectra were acquired at positions corresponding to different nominal Ba/Sr stoichiometry. In all measurements, the Ba 3d5/2 core-level spectra can be represented by two main components, i.e. one component at higher binding energy (BE = 780.54 eV) corresponding to surface contribution and the other one at lower binding energy (BE = 778.92 eV) corresponding to sub-surface contribution (Figs. 2 and 3). Going from normal to 60° emission angle and using a 3-unit cell thick film model, the surface to sub-surface intensity ratio clearly evolves providing evidence of a Ba-rich surfactant. The surfactant effect is more significant for lower nominal Ba stoichiometry.

We improved lake mixing process simulations by applying a vertical mixing scheme, K profile parameterization (KPP), in the Community Land Model (CLM) version 4.5, developed by the National Center for Atmospheric Research. Vertical mixing of the lake water column can significantly affect heat transfer and vertical temperature profiles. However, the current vertical mixing scheme in CLM requires an arbitrarily enlarged eddy diffusivity to enhance water mixing. The coupled CLM-KPP considers a boundary layer for eddy development, and in the lake interior water mixing is associated with internal wave activity and shear instability. We chose a lake in Arctic Alaska and a lake on the Tibetan Plateau to evaluate this improved lake model. Results demonstrated that CLM-KPP reproduced the observed lake mixing and significantly improved lake temperature simulations when compared to the original CLM. Our newly improved model better represents the transition between stratification and turnover. This improved lake model has great potential for reliable physical lake process predictions and better ecosystem services.

In the late 1970s and ’80s, a new generation of Chinese poets emerged with a powerful critique of the state’s aggressive political reforms. After the 1976 Tiananmen Square incident, the Bejing poet Zaho Zhenkai (known as Bei Dao) wrote a startling poem titled “The Answer” about his refusal to believe in the unquestioned ultimacy of China’s worldview. Bei Dao’s unique style of poetry helped readers make new associations that were otherwise inaccessible to them. This article examines Bei Dao’s use of metaphor in “The Answer” through the lens of the aesthetic philosopher Lambert Zuidervaart and suggests that the poet’s use of self-controverting metaphors makes an absent reality graspable and present. The article then considers the role of public theology as it listens to the witness of the poet’s bewildering evocation of accessing “the real” through disbelief. In consideration of Herman Bavinck’s essay On Contemporary Ethics, this article suggests that theologians (and religious practitioners) should resist the temptation to control the artist’s expression even when it limps with narcissism and moral deficiency. Instead, the theologian (and the church) should fight alongside the artist in helping them to share their staggering vision or, in Bei Dao’s case, the transcendent power of resiliency sustained by the shadows of the dead. This article aims to generate a fruitful dialogue between Bei Dao and the Reformed theological tradition that underscores the uncanny importance of disbelief as an alternative strategy for cultural transformation and faithful proclamation.

We have studied the field cycling behavior of microscopic TiN/Hf0.5Zr0.5O2/TiN ferroelectric capacitors using synchrotron-based soft x-ray photoemission electron microscopy. The oxygen vacancy ([Formula: see text]) concentration near the top TiN/Hf0.5Zr0.5O2 interface is estimated from the reduction of Hf4+ to Hf3+ as measured in the Hf 4f core level spectra. The [Formula: see text] concentration increases with field cycling and redistributes under the effect of the internal field due to the polarization. Upward pointing polarization slightly depletes the concentration near the top interface, whereas downward polarization causes [Formula: see text] drift toward the top interface. The [Formula: see text] redistribution after wake-up is consistent with shifts in the I–V switching peak. The Schottky barrier height for electrons decreases systematically with cycling in polarization states, reflecting the overall increase in [Formula: see text].

BackgroundTraining procedural skills using proficiency-based progression (PBP) methodology has consistently resulted in error reduction. We hypothesised that implementation of metric-based PBP training and a valid assessment tool would decrease the failure rate of epidural analgesia during labour when compared to standard simulation-based training.MethodsDetailed, procedure-specific metrics for labour epidural catheter placement were developed based on carefully elicited expert input. Proficiency was defined using criteria derived from clinical performance of experienced practitioners. A PBP curriculum was developed to train medical personnel on these specific metrics and to eliminate errors in a simulation environment.Seventeen novice anaesthetic trainees were randomly allocated to undergo PBP training (Group P) or simulation only training (Group S). Following training, data from the first 10 labour epidurals performed by each participant were recorded. The primary outcome measure was epidural failure rate.ResultsA total of 74 metrics were developed and validated. The inter-rater reliability (IRR) of the derived assessment tool was 0.88. Of 17 trainees recruited, eight were randomly allocated to group S and six to group P (three trainees did not complete the study). Data from 140 clinical procedures were collected. The incidence of epidural failure was reduced by 54% with PBP training (28.7% in Group S vs 13.3% in Group P, absolute risk reduction 15.4% with 95% CI 2% to 28.8%, p=0.04).ConclusionProcedure-specific metrics developed for labour epidural catheter placement discriminated the performance of experts and novices with an IRR of 0.88. Proficiency-based progression training resulted in a lower incidence of epidural failure compared to simulation only training.Trial registration numberNCT02179879.NCT02185079; Post-results.

The domain structure of uniaxial ferroelectric lithium niobate single crystals is investigated using Raman spectroscopy mapping. The influence of doping with magnesium and poling at room temperature is studied by analysing frequency shifts at domain walls and their variations with dopant concentration and annealing conditions. It is shown that defects are stabilized at domain walls and that changes in the defect structures with Mg concentration can be probed by the shift of Raman modes. We show that the signatures of polar defects in the bulk and at the domain walls differ., 10 pages, 3 figures

Ferroic domain walls could play an important role in microelectronics, given their nanometric size and often distinct functional properties. Until now, devices and device concepts were mostly based on mobile domain walls in ferromagnetic and ferroelectric materials. A less explored path is to make use of polar domain walls in nonpolar ferroelastic materials. Indeed, while the polar character of ferroelastic domain walls has been demonstrated, polarization control has been elusive. Here, we report evidence for the electrostatic signature of the domain-wall polarization in nonpolar calcium titanate (CaTiO3). Macroscopic mechanical resonances excited by an ac electric field are observed as a signature of a piezoelectric response caused by polar walls. On the microscopic scale, the polarization in domain walls modifies the local surface potential of the sample. Through imaging of surface potential variations, we show that the potential at the domain wall can be controlled by electron injection. This could enable devices based on nondestructive information readout of surface potential., Comment: 30 pages, 12 figures

The effects of the bonding mechanism and band alignment in a ferroelectric (FE) BaTiO3/ferromagnetic La0.6Sr0.4MnO3 heterostructure are studied using x-ray photoelectron spectroscopy and first-principles calculations. The band lineup at the interface is determined by a combination of band bending and polarization-induced modification of core-hole screening. A Schottky barrier height for electrons of 1.22 ± 0.17 eV is obtained in the case of downwards FE polarization of the top layer. The symmetry of the bonding states is emphasized by integrating the local density of states ±0.2 eV around the Fermi level, and strong dependence on the FE polarization is found: upwards, polarization stabilizes Ti t2g(xy) orbitals, while downwards, polarization favors Ti t2g(yz) symmetry. It is predicted that the abrupt (La,Sr)|TiO2 interface is magnetoelectrically active, leading to a A-type antiferromagnetic coupling of the first TiO2 interface layer with the underlying manganite layer through a superexchange mechanism

We implemented high-resolution photoelectron spectroscopy using synchrotron radiation (160 eV photon energy) to investigate the electronics and chemistry at the interfaces of HfO2 (1 nm)/GeOxNy (0.6 nm)/Ge gate stacks. Ge3d core-level spectra show the formation of Hf-germanate at the bottom Ge oxide-high κ interface. Valence-band spectra highlight the presence of electronic N2p states in the Ge oxide band gap. The GeON/Ge valence band offset is determined as 1 eV{plus minus}0.2 eV.

International audience; The presence of gold on the sidewall of a tapered, single silicon nanowire is directly quantified from core-level nanospectra using energy- filtered photoelectron emission microscopy. The uniform island-type partial coverage of gold determined as 0.42 +/- 0.06 (∼1.8 ML) is in quantitative agreement with the diameter reduction of the gold catalyst observed by scanning electron microscopy and is confirmed by a splitting of the photothresholds collected from the sidewall, from which characteristic local work functions are extracted using a model of the full secondary electron distributions.

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The Mo 50 Ni 50 system has been prepared by mechanical alloying, starting from a mixture of pure crystalline elements. Contrary to the case of meltquenching methods, an amorphous Mo x Ni 1− x phase has been observed after milling. A structural study by X-ray diffraction and EXAFS has shown that nickel atoms are already totally involved in the solid-state amorphization reaction after 10 h, whereas more milling time is needed to amorphize the residual crystalline b.c.c. molybdenum. Because of the relatively low ΔH for calculated according to thermodynamic models for this system, the requirement of a strong negative heat of formation as a necessary condition for amorphization does not seem to be very stringent.

In the past decade, oxide-based heterostructures have been studied extensively as potentially attractive systems for applications in nanoelectronics. Among them, ferroelectric materials raised interest as potential support for those technological applications. Indeed, their spontaneous electric polarization easily switched by applying an electric field makes them a good basis for non-volatile data storage. Switching the polarization requires a metallic contact with an electrode, thus heterostructures of ferroelectric thin films with metallic electrodes have been widely studied. At the interface between those two materials, free charges of the electrode help screening the polarization induced surface charges detrimental to maintaining proper polarization in the ferroelectric thin film. With metallic oxide electrodes, an ionic displacement at the electrode/ferroelectric interface will help the screening. However, despite important theoretical discoveries, direct experimental data is scarce and further understanding of the interface behavior is crucial for a proper integration of ferroelectric films in functioning nanometer sized devices. In this thesis, photoemission spectroscopy based techniques are used to probe the buried interface of an electrode/BaTiO₃/electrode heterostructure, for two different electrodes: the metallic oxide SrRuO₃ and the Co metal. We acquired information on the behavior of the interface and its response to polarization switching. This work is a new step towards a complete understanding on the behavior of the interface between electrodes and the BaTiO₃ ferroelectric, in device-like heterostructures, in terms of electronic properties, kinetic, and fatigue. The experiments presented combined state of the art characterization techniques, where the use of hard X-rays and in situ bias application made it possible to resolve the difficult task of probing buried interfaces in working conditions., Au cours des dix dernières années, les hétérostructures à base de matériaux oxyde ont été grandement étudiées comme potentiel systèmes d’application pour le nanoélectronique. Parmi eux, les ferroélectriques (FE) sont particulièrement intéressants comme support pour ces applications technologies. En effet, leur polarisation électrique spontanée, aisément réversible par application d’un champ électrique en fait de bons candidats pour le stockage de données non-volatile. Renverser la polarisation nécessite un contact avec une électrode, ainsi les hétérostructures de films mince de FE avec électrodes métalliques ont été grandement étudiées. A l’interface entre les deux matériaux, les charges libres de l’électrode permettent d’écranter les charges de surfaces, détrimentales au maintien de la polarisation au sein du film FE. Avec des électrodes d’oxyde métalliques, un déplacement ionique à l’interface électrode/FE va d’avantage favoriser cet écrantage, plaçant l’interface au cœur du processus d’écrantage. Cependant, malgré d’importantes découvertes théoriques, les données expérimentales sont rares et le comportement exact de l’interface électrode/FE est seulement partiellement maitrisée. Une plus grande compréhension est indispensable pour une intégration correcte des films FE dans des dispositifs nanométriques. Dans cette thèse, des techniques basées sur la spectroscopie de photoémission sont utilisées pour sonder l’interface enfouie d’une hétérostructure électrode/BaTiO₃/électrode, dans le cas de deux électrodes différentes : l’oxyde métallique SrRuO₃ et le métal cobalt. Nous avons acquis des informations sur le comportement de l’interface et sa réponse au renversement de la polarisation. Ce travail est un nouveau pas vers une plus grande maitrise des phénomènes physiques gouvernant le comportement de l’interface entre électrodes le ferroélectrique BaTiO₃, en termes de propriété électronique, de cinétique et de fatigue. Les expériences présentées couplent des techniques d’analyses de pointes, où l’utilisation de rayons X durs et l’application de champs électriques in situ ont rendus possible la difficile tâche de sonder des interfaces enfouies en condition de fonctionnement.

This thesis addresses the problem of imaging of model systems planar silicon pn junctions, fabricated by localized epitaxy, using the novel energy-filtered X-ray PhotoElectron Emission Microscope (XPEEM). The objective is to improve the understanding of the phenomena influencing the XPEEM images of the junctions, with as long-term perspective, a possible application of this method in a complementary way to existing techniques of 2D dopant mapping. The studies were carried out over three types of junction realized to this purpose and presenting variable electrical field (P+/P, N+/P, P+/N). We firstly developed and optimized a passivation protocol in three-steps which yielded a surface close to flat band conditions. This process allowed us to deduce band alignments as a function of doping level and type on both side of the junction thanks to spectroscopic XPEEM imaging of secondary electrons (to determine local work function), Si 2p core-level and valence band with both laboratory photon sources and synchrotron radiation. Contrast in core-level imaging due to the first atomic layer of the surface was also shown. Then, we highlighted the role of the lateral electric field across the depletion zone of a pn junction which shifts the apparent position of the latter in PEEM imaging. We compared experimental results and simulations performed with SIMION software to estimate the influence of pn junctions on PEEM imaging. Dark field imaging of the junction was also simulated. Comparison with the experimental results showed that it can be used to localize the real junction., Ce mémoire de thèse traite de l'étude de jonctions pn silicium planaires, réalisées par épitaxie localisée, avec un nouveau type de microscopie à émission de photoélectrons (XPEEM) filtré en énergie. L'objectif est d'améliorer notre compréhension des facteurs influençant l'imagerie XPEEM de jonctions modèles avec une perspective à plus long terme d'application de cette technique aux cas réels. Sur les trois types de jonction réalisées présentant des champs électriques variables P+/P, N+/P, P+/N), nous avons d'abord mis en oeuvre un procédé de passivation en trois étapes afin de se rapprocher de conditions en bandes plates en surface. Ce procédé nous a permis d'étudier la position des niveaux électroniques de part et d'autre des jonctions grâce à une imagerie en XPEEM spectroscopique avec électrons secondaires (travail de sortie local), électrons de coeur Si 2p et bande de valence, avec à la fois avec des sources X de laboratoire et le rayonnement synchrotron. Un mécanisme de contraste des images en électrons de coeur dû à la toute première couche atomique de surface a été montré. Ensuite, nous avons mis en évidence le rôle du champ électrique au niveau de la zone de déplétion des jonctions qui décale la position apparente de cette dernière dans l'image XPEEM. Nous avons comparé les résultats expérimentaux avec des simulations (logiciel SIMION) afin d'estimer son influence sur les conditions d'imagerie. Enfin, nous avons étudié l'impact de la technique d'imagerie en champ sombre sur la localisation de la jonction réelle au niveau de la surface de l'échantillon.