arXiv subjects

Simon J. L. Billinge

Publications and source records attributed to Simon J. L. Billinge.

68 records · Page 4Linked to original sources

arXiv2013

Evidence for Fluctuating Charge Stripes far above the Charge-Ordering Transition in La$_{1.67}$ Sr$_{0.33}$ NiO$_{4}$

The temperature evolution of structural effects associated with charge (CO) and spin order (SO) in La$_{1.67}$Sr$_{0.33}$NiO$_{4}$ has been investigated using neutron powder diffraction. We report an anomalous shrinking of the $c/a$ lattice parameter ratio that correlates with $T_{\rm CO}$. The sign of this change can be explained by the change in interlayer Coulomb energy between the static stripe-ordered state and the fluctuating stripe-ordered state or the charge-disordered state. In addition, we identify a contribution to the mean-square displacements of Ni and in-plane O atoms whose width correlates quite well with the size of the pseudogap extracted from the reported optical conductivity, with a non-Debye-like component that persists below and well above $T_{\rm CO}$. We infer that dynamic charge-stripe correlations survive to $T\sim2T_{\rm CO}$

cond-mat.str-el↗

arXiv2012

PDFgetX3: A rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions

PDFgetX3 is a new software application for converting X-ray powder diffraction data to atomic pair distribution function (PDF). PDFgetX3 has been designed for ease of use, speed and automated operation. The software can readily process hundreds of X-ray patterns within few seconds and is thus useful for high-throughput PDF studies, that measure numerous datasets as a function of time, temperature or other environment parameters. In comparison to the preceding programs, PDFgetX3 requires fewer inputs, less user experience and can be readily adopted by novice users. The live-plotting interactive feature allows to assess the effects of calculation parameters and select their optimum values. PDFgetX3 uses an ad-hoc data correction method, where the slowly-changing structure independent signal is filtered out to obtain coherent X-ray intensities that contain structure information. The outputs from PDFgetX3 have been verified by processing experimental PDFs from inorganic, organic and nanosized samples and comparing them to their counterparts from previous established software. In spite of different algorithm, the obtained PDFs were nearly identical and yielded highly similar results when used in structure refinement. PDFgetX3 is written in Python language and features well documented, reusable codebase. The software can be used either as standalone application or as a library of PDF-processing functions that can be called on from other Python scripts. The software is free for open academic research, but requires paid license for commercial use.

cond-mat.mtrl-sci↗

arXiv2012

Towards a robust ad-hoc data correction approach that yields reliable atomic pair distribution functions from powder diffraction data

We examine the equations to obtain atomic pair distribution functions (PDFs) from x-ray, neutron and electron powder diffraction data with a view to obtaining reliable and accurate PDFs from the raw data using a largely \emph{ad hoc} correction process. We find that this should be possible under certain circumstances that hold, to a reasonably good approximation, in many modern experiments. We describe a variational approach that could be applied to find data correction parameters that is highly automatable and should require little in the way of user inputs yet results in quantitatively reliable PDFs, modulo unknown scale factors that are often not of scientific interest when profile fitting models are applied to the data with scale-factor as a parameter. We have worked on a particular implementation of these ideas and demonstrate that it yields PDFs that are of comparable quality to those obtained with existing x-ray data reduction program PDFgetX2. This opens the door to rapid and highly automated processing of raw data to obtain PDFs.

cond-mat.mtrl-sci↗

arXiv2012

Local structure of ReO$_3$ at ambient pressure from neutron total scattering study

A hypothesis that the local rotations of ReO$_6$ octahedra persist in the crystallographically untilted ambient phase of ReO$_3$ is examined by the high-resolution neutron time-of-flight total scattering based atomic pair distribution function analysis. Three candidate models were tested, Pm$\bar{3}$m, P4/mbm, and Im$\bar{3}$, for the local structure of ReO$_3$ at ambient pressure and 12 K, and both quantitative and qualitative assessment of the data were performed. No evidence for large local octahedral rotations was found, suggesting that the local and the average structure are the same (Pm$\bar{3}$m) as normally assumed.

cond-mat.mtrl-sci↗

arXiv2012

Lattice dynamics reveals a local symmetry breaking in the emergent dipole phase of PbTe

Local symmetry breaking in complex materials is emerging as an important contributor to materials properties but is inherently difficult to study. Here we follow up an earlier structural observation of such a local symmetry broken phase in the technologically important compound PbTe with a study of the lattice dynamics using inelastic neutron scattering (INS). We show that the lattice dynamics are responsive to the local symmetry broken phase, giving key insights in the behavior of PbTe, but also revealing INS as a powerful tool for studying local structure. The new result is the observation of the unexpected appearance on warming of a new zone center phonon branch in PbTe. In a harmonic solid the number of phonon branches is strictly determined by the contents and symmetry of the unit cell. The appearance of the new mode indicates a crossover to a dynamic lower symmetry structure with increasing temperature. No structural transition is seen crystallographically but the appearance of the new mode in inelastic neutron scattering coincides with the observation of local Pb off-centering dipoles observed in the local structure. The observation resembles relaxor ferroelectricity but since there are no inhomogeneous dopants in pure PbTe this anomalous behavior is an intrinsic response of the system. We call such an appearance of dipoles out of a non-dipolar ground-state "emphanisis" meaning the appearance out of nothing. It cannot be explained within the framework of conventional phase transition theories such as soft-mode theory and challenges our basic understanding of the physics of materials.

cond-mat.mtrl-sci↗

arXiv2012

Quantitative nanostructure characterization using atomic pair distribution functions obtained from laboratory electron microscopes

Quantitatively reliable atomic pair distribution functions (PDFs) have been obtained from nanomaterials in a straightforward way from a standard laboratory transmission electron microscope (TEM). The approach looks very promising for making electron-derived PDFs (ePDFs) a routine step in the characterization of nanomaterials because of the ubiquity of such TEMs in chemistry and materials laboratories. No special attachments such as energy filters were required on the microscope. The methodology for obtaining the ePDFs is described as well as some opportunities and limitations of the method.

cond-mat.mtrl-sci↗

arXiv2011

Synthesis, crystal structure and magnetism of beta-Fe1.00(2)Se1.00(3) single crystals

Understanding iron based superconductors requires high quality impurity free single crystals. So far they have been elusive for beta-FeSe and extraction of intrinsic materials properties has been compromised by several magnetic impurity phases. Herein we report synchrotron - clean beta-FeSe superconducting single crystals grown via LiCl/CsCl flux method. Phase purity yields evidence for a defect induced weak ferromagnetism that coexists with superconductivity below Tc. In contrast to Fe1+yTe - based superconductors, our results reveal that the interstitial Fe(2) site is not occupied and that all contribution to density of states at the Fermi level must come from in-plane Fe(1).

cond-mat.supr-con↗

arXiv2011

The Nyquist-Shannon sampling theorem and the atomic pair distribution function

We have systematically studied the optimal real-space sampling of atomic pair distribution data by comparing refinement results from oversampled and resampled data. Based on nickel and a complex perovskite system, we demonstrate that the optimal sampling is bounded by the Nyquist interval described by the Nyquist-Shannon sampling theorem. Near this sampling interval, the data points in the PDF are minimally correlated, which results in more reliable uncertainty prediction. Furthermore, refinements using sparsely sampled data may run many times faster than using oversampled data. This investigation establishes a theoretically sound limit on the amount of information contained in the PDF, which has ramifications towards how PDF data are modeled.

cond-mat.mtrl-sci↗

arXiv2010

Crystal structure solution from experimentally determined atomic pair distribution functions

The paper describes an extension of the Liga algorithm for structure solution from atomic pair distribution function (PDF), to handle periodic crystal structures with multiple elements in the unit cell. The procedure is performed in 2 separate steps - at first the Liga algorithm is used to find unit cell sites consistent with pair distances extracted from the experimental PDF. In the second step the assignment of atom species over cell sites is solved by minimizing the overlap of their empirical atomic radii. The procedure has been demonstrated on synchrotron x-ray PDF data from 16 test samples. The structure solution was successful for 14 samples including cases with enlarged super cells. The algorithm success rate and the reasons for failed cases are discussed together with enhancements that should improve its convergence and usability.

cond-mat.mtrl-sci↗

arXiv2009

Quantitative nanoparticle structures from ultrafast electron crystallography data

We describe the quantitative refinement of nanoparticle structures from gold nanoparticles probed by ultrafast electron crystallography (UEC). We establish the equivalence between the modified radial distribution function employed in UEC and the atomic pair distribution function (PDF) used in x-ray and neutron powder diffraction analysis. By leveraging PDF refinement techniques, we demonstrate that UEC data are of sufficient quality to differentiate between cuboctahedral, decahedral and icosahedral nanoparticle models. Furthermore, we identify the signatures of systematic errors that may occur during data reduction and show that atomic positions refined from UEC are robust to these errors. This work serves as a foundation for reliable quantitative structural analysis of time-resolved laser-excited nanoparticle states.

cond-mat.mtrl-sci↗

arXiv2008

Relationship between the atomic pair distribution function and small angle scattering: implications for modeling of nanoparticles

Here we show explicitly the relationship between the functions used in the atomic pair distribution function (PDF) method and those commonly used in small angle scattering (SAS) analyses. The origin of the sloping baseline, $-4πrρ_0$, in PDFs of bulk materials is identified as originating from the SAS intensity that is neglected in PDF measurements. The non-linear baseline in nanoparticles has the same origin, and contains information about the shape and size of the nanoparticles.

cond-mat.mtrl-sci↗

arXiv2007

Nature of the Monoclinic to Cubic Phase Transition in the Fast Oxygen Ion Conductor La2Mo2O9 (LAMOX)

La2Mo2O9 (LAMOX) is a fast oxygen ion conductor which shows high oxygen ion conductivities comparable to those of yttria-sabilized zirconia (YSZ) . LAMOX is subject to a structural phase transition from the non-conductive monoclinic form to the highly-conductive cubic form at about 580C. The origin of the conductivity in cubic LAMOX has been suggested to be due to a "disorder" in the O sub-lattice without any insight into the real distribution of the oxygen ion. In this paper, thanks to the application of the neutron atomic pair distribution function (PDF) analysis, we provided evidences that the local structure of the cubic polymorph of LAMOX is exactly the same of that of the monoclinic phase thus indicating that the structural phase transition is actually a transition from a static to a dynamic distribution of the oxygen defects. This work represent the first application of the atomic-pair distribution function analysis to the study of an oxygen fast-oxide ion conductor and clearly indicates that a more reliable and detailed description of their local structure, particularly in the highly conductive phases, and can lead to a better comprehension of the structure-property correlation, which is the starting point for the design of new and optimized functional materials.

cond-mat.mtrl-sci↗

arXiv2003

Evidence for nano-scale inhomogeneities in bilayer manganites in the Mn\sp{4+} rich region: $\bm{0.54 \leq x \leq 0.80}$

The atomic pair distribution function (PDF) technique is employed to probe the atomic local structural responses in naturally double layered manganites \lsmo in the doping range $0.54 \leq x \leq 0.80$. Our low temperature neutron powder diffraction measurements suggest the coexistence of two different Jahn-Teller (JT) distorted MnO$_6$ octahedra when its ordered magnetic structure crosses over from type A ($0.54 \leq x \leq 0.66$) to type C/C$^*$ ($0.74 \leq x \leq 0.90$) ordering. At all doping levels at low temperature the doped holes reside predominantly in the plane of the bilayer. In the type A magnetic ordering regime, the e$_g$ electrons appear to be significantly delocalized in the plane resulting in undistorted octahedra, while in type C/C$^*$ regime, elongated JT distorted octahedra are apparent. This is consistent with the presence of inhomogeneous coexisting delocalized and localized electronic states. No evidence of macroscopic phase separation has been observed. Such nanoscale inhomogeneities may explain the magnetically frustrated behavior observed in the spin disordered ``gap'' region ($0.66 \leq x \leq 0.74$).

cond-mat.str-el↗

arXiv2003

Rapid Acquisition Pair Distribution Function (RA-PDF) Analysis

An image plate (IP) detector coupled with high energy synchrotron radiation was used for atomic pair distribution function (PDF) analysis, with high probed momentum transfer \Qmax $\leq 28.5$ \RAA from crystalline materials. Materials with different structural complexities were measured to test the validity of the quantitative data analysis. Experimental results are presented here for crystalline Ni, crystalline \alf, and the layered Aurivillius type oxides \bivo and \bivtio . Overall, the diffraction patterns show good counting statistics with measuring time from one to tens of seconds. The PDFs obtained are of high quality. Structures may be refined from these PDFs, and the structural models are consistent with the published literature. Data sets from similar samples are highly reproducible.

cond-mat↗