The Developmental Chronnecto-Genomics (Dev-CoG) study: A multimodal study on the developing brain.

Brain development has largely been studied through unimodal analysis of neuroimaging data, providing independent results for structural and functional data. However, structure clearly impacts function and vice versa, pointing to the need for performing multimodal data collection and analysis to improve our understanding of brain development, and to further inform models of typical and atypical brain development across the lifespan. Ultimately, such models should also incorporate genetic and epigenetic mechanisms underlying brain structure and function, although currently this area is poorly specified. To this end, we are reporting here a multi-site, multi-modal dataset that captures cognitive function, brain structure and function, and genetic and epigenetic measures to better quantify the factors that influence brain development in children originally aged 9-14 years. Data collection for the Developmental Chronnecto-Genomics (Dev-CoG) study (http://devcog.mrn.org/) includes cognitive, emotional, and social performance scales, structural and functional MRI, diffusion MRI, magnetoencephalography (MEG), and saliva collection for DNA analysis of single nucleotide polymorphisms (SNPs) and DNA methylation patterns. Across two sites (The Mind Research Network and the University of Nebraska Medical Center), data from over 200 participants were collected and these children were re-tested annually for at least 3 years. The data collection protocol, sample demographics, and data quality measures for the dataset are presented here. The sample will be made freely available through the collaborative informatics and neuroimaging suite (COINS) database at the conclusion of the study.

Dynamic layer rearrangement during growth of layered oxide films by molecular beam epitaxy.

The A(n+1)B(n)O(3n+1) Ruddlesden-Popper homologous series offers a wide variety of functionalities including dielectric, ferroelectric, magnetic and catalytic properties. Unfortunately, the synthesis of such layered oxides has been a major challenge owing to the occurrence of growth defects that result in poor materials behaviour in the higher-order members. To understand the fundamental physics of layered oxide growth, we have developed an oxide molecular beam epitaxy system with in situ synchrotron X-ray scattering capability. We present results demonstrating that layered oxide films can dynamically rearrange during growth, leading to structures that are highly unexpected on the basis of the intended layer sequencing. Theoretical calculations indicate that rearrangement can occur in many layered oxide systems and suggest a general approach that may be essential for the construction of metastable Ruddlesden-Popper phases. We demonstrate the utility of the new-found growth strategy by performing the first atomically controlled synthesis of single-crystalline La3Ni2O7.

Nucleation and growth of epitaxial metal-oxide films based on polymer-assisted deposition.

Polymer-assisted deposition (PAD) is one of the chemical solution deposition methods which have been successfully used to grow films, form coatings, and synthesize nanostructured materials. In comparison with other conventional solution-based deposition techniques, PAD differs in its use of water-soluble polymers in the solution that prevent the metal ions from unwanted chemical reactions and keep the solution stable. Furthermore, filtration to remove non-coordinated cations and anions in the PAD process ensures well controlled nucleation, which enables the growth of high quality epitaxial films with desired structural and physical properties. The precursor solution is prepared by mixing water-soluble polymer(s) with salt(s). Thermal treatment of the precursor films in a controlled environment leads to the formation of desired materials. Using BaTiO3 grown on SrTiO3 and LaMnO3 on LaAlO3 as model systems, we show the effect of filtration on the nucleation and growth of epitaxial complex metal-oxide films based on the PAD process.

Modular instrument mounting system for variable environment in operando X-ray experiments.

In the growing field of in operando and in situ X-ray experiments, there exists a large disparity in the types of environments and equipment to control them. This situation makes it challenging to conduct multiple experiments with a single mechanical interface to the diffractometer. Here, we describe the design and implementation of a modular instrument mounting system that can be installed on a standard six-circle diffractometer (e.g., 5021 Huber GmbH). This new system allows for the rapid changeover of different chambers and sample heaters and permits accurate sample positioning (x, y, z, and azimuthal rotation) without rigid coupling to the chamber body. Isolation of the sample motion from the chamber enclosure is accomplished through a combination of custom rotary seals and bellows. Control of the pressure and temperature has been demonstrated in the ranges of 10(-6)-10(3) Torr and 25°C-900°C, respectively. We have utilized the system with several different modular instruments. As an example, we provide in situ sputtering results, where the growth dynamics of epitaxial LaGaO3 thin films on (001) SrTiO3 substrates were investigated.

Equilibrium polarization of ultrathin PbTiO3 with surface compensation controlled by oxygen partial pressure.

We present a synchrotron x-ray study of the equilibrium polarization structure of ultrathin PbTiO(3) films on SrRuO(3) electrodes epitaxially grown on SrTiO(3) (001) substrates, as a function of temperature and the external oxygen partial pressure (pO(2)) controlling their surface charge compensation. We find that the ferroelectric Curie temperature (T(C)) varies with pO(2) and has a minimum at the intermediate pO(2), where the polarization below T(C) changes sign. The experiments are in qualitative agreement with a model based on Landau theory that takes into account the interaction of the phase transition with the electrochemical equilibria for charged surface species. The paraelectric phase is stabilized at intermediate pO(2) when the concentrations of surface species are insufficient to compensate either polar orientation.

Total-reflection inelastic X-ray scattering from a 10-nm thick La0.6Sr0.4CoO3 thin film.

To study equilibrium changes in composition, valence, and electronic structure near the surface and into the bulk, we demonstrate the use of a new approach, total-reflection inelastic x-ray scattering, as a sub-keV spectroscopy capable of depth profiling chemical changes in thin films with nanometer resolution. By comparing data acquired under total x-ray reflection and penetrating conditions, we are able to separate the O K-edge spectra from a 10 nm La0.6Sr0.4CoO3 thin film from that of the underlying SrTiO3 substrate. With a smaller wavelength probe than comparable soft x-ray absorption measurements, we also describe the ability to easily access dipole-forbidden final states, using the dramatic evolution of the La N4,5 edge with momentum transfer as an example.

Ferroelectricity in ultrathin BaTiO3 films: probing the size effect by ultraviolet Raman spectroscopy.

We demonstrate the dramatic effect of film thickness on the ferroelectric phase transition temperature Tc in strained BaTiO3 films grown on SrTiO3 substrates. Using variable-temperature ultraviolet Raman spectroscopy enables measuring Tc in films as thin as 1.6 nm, and a film thickness variation from 1.6 to 10 nm leads to Tc tuning from 70 to about 925 K. Raman data are consistent with synchrotron x-ray scattering results, which indicate the presence of 180 degrees domains below Tc, and thermodynamic phase-field model calculations of Tc as a function of thickness.

Reversible chemical switching of a ferroelectric film.

According to recent experiments and predictions, the orientation of the polarization at the surface of a ferroelectric material can affect its surface chemistry. Here we demonstrate the converse effect: the chemical environment can control the polarization orientation in a ferroelectric film. In situ synchrotron x-ray scattering measurements show that high or low oxygen partial pressure induces outward or inward polarization, respectively, in an ultrathin PbTiO3 film. Ab initio calculations provide insight into surface structure changes observed during chemical switching.

Cu2O island shape transition during Cu-Au alloy oxidation.

In situ transmission electron microscopy observations of the oxidation of (001) Cu-Au alloys indicate that the Cu2O islands that form undergo a remarkable transformation from an initially compact morphology to a dendritic structure as growth proceeds. Correspondingly, the surface composition becomes nonuniform and the fractal dimension associated with the islands evolves from 2.0 to a stable value of 1.87, indicating a transition in the rate-limiting mechanism of oxidation from oxygen surface diffusion to diffusion of copper through the increasingly gold-rich regions adjacent to the islands.

Stabilization of monodomain polarization in ultrathin PbTiO3 films.

Using in situ high-resolution synchrotron x-ray scattering, the Curie temperature TC has been determined for ultrathin c-axis epitaxial PbTiO3 films on conducting substrates (SrRuO3 on SrTiO3), with surfaces exposed to a controlled vapor environment. The suppression of TC was relatively small, even for the thinnest film (1.2 nm). We observe that 180 degrees stripe domains do not form, indicating that the depolarizing field is compensated by free charge at both interfaces. This is confirmed by ab initio calculations that find polar ground states in the presence of ionic adsorbates.

In situ synchrotron X-ray studies of ferroelectric thin films.

In situ synchrotron X-ray scattering was used to observe both the growth of PbTiO3 films by metal-organic chemical vapour deposition and the behaviour of the ferroelectric phase transition as a function of film thickness. The dependences of growth mode and deposition rate on gas flows and substrate temperature were determined by homoepitaxial growth studies on thick films (>50 nm). These studies facilitated the growth of thin coherently strained PbTiO3 films on SrTiO3 (001) substrates, with thicknesses ranging from 2 to 42 nm. Experiments on the ferroelectric phase transition as a function of film thickness were carried out in these films under controlled mechanical and electrical boundary conditions.

Observation of nanoscale 180 degrees stripe domains in ferroelectric PbTiO3 thin films.

We report the observation of periodic 180 degrees stripe domains below the ferroelectric transition in thin films. Epitaxial PbTiO3 films of thickness d=1.6 to 42 nm on SrTiO3 substrates were studied using x-ray scattering. Upon cooling below T(C), satellites appeared around Bragg peaks indicating the presence of 180 degrees stripe domains of period Lambda=3.7 to 24 nm. The dependence of Lambda on d agrees well with theory including epitaxial strain effects, while the suppression of T(C) for thinner films is significantly larger than that expected solely from stripe domains.

Antiferrodistortive reconstruction of the PbTiO(3)(001) surface.

We present in situ x-ray scattering measurements of the surface structures of PbTiO(3) (001) in equilibrium with PbO vapor. At 875 to 1025 K, a reconstruction having c(2x2) symmetry is present under most conditions, while a 1 x 6 reconstruction occurs under PbO-poor conditions. The atomic structure of the c(2x2) phase is found to consist of a single layer of an antiferrodistortive structure with oxygen cages counter-rotated by 10 degrees about the titanium ions.