General approaches for shear-correcting coordinate transformations in Bragg coherent diffraction imaging: Part 2

X-ray Bragg coherent diffraction imaging has been demonstrated as a powerful three-dimensional (3D) microscopy approach for the investigation of sub-micrometer-scale crystalline particles. It is based on the measurement of a series of coherent diffraction intensity patterns that are numerically inverted to retrieve an image of the spatial distribution of relative phase and amplitude of the Bragg structure factor of the scatterer. This 3D information, which is collected through an angular rotation of the sample, is necessarily obtained in a non-orthogonal frame in Fourier space that must be eventually reconciled. To deal with this, the currently favored approach (detailed in Part I) is to perform the entire inversion in conjugate non-orthogonal real and Fourier space frames, and to transform the 3D sample image into an orthogonal frame as a post-processing step for result analysis. In this article, a direct follow-up of Part I, we demonstrate two different transformation strategies that enable the entire inversion procedure of the measured data set to be performed in an orthogonal frame. The new approaches described here build mathematical and numerical frameworks that apply to the cases of evenly and non-evenly sampled data along the direction of sample rotation (the rocking curve). The value of these methods is that they rely on and incorporate significantly more information about the experimental geometry into the design of the phase retrieval Fourier transformation than the strategy presented in Part I. Two important outcomes are 1) that the resulting sample image is correctly interpreted in a shear-free frame, and 2) physically realistic constraints of BCDI phase retrieval that are difficult to implement with current methods are easily incorporated. Computing scripts are also given to aid readers in the implementation of the proposed formalisms

Structural Evolution of a Cyclooctatetraene Adlayer on Cu(111) during Isothermal Desorption

The use of helium diffraction patterns to study desorption processes is explored as a novel extension to traditional methods based on helium specular reflection. The sample, cyclooctatetraene adsorbed on Cu(111), provides a rich but complex structure. The modulation of cyclooctatetraene by Cu(111) is manifested as a convolution in the diffraction pattern, displaying an averaged super-cell symmetry of (7 √3 × 7 √3)R30◦. The adlayer expands during isothermal desorption, and the change in lattice constant provides a direct measure of the coverage as a function of time. We find a desorption energy of 0:96 ± 0:01 eV at saturation of the first layer, and an upper limit of 1:62 ± 0:07 eV for isolated molecules. These values, and details of the assigned structure, indicate chemisorbed molecules with a planar conformation.For financial support, N. Avidor gratefully acknowledges the Blavatnik Foundation, J.A. Lau acknowledges the ICASEC, P.S.M. Townsend acknowledges the UK EPSRC, I. Calvo-Almaz´an acknowledges the Ram´on Areces Foundation, BJ Hinch acknowledges the NSF (CHE-1565673). The authors thank G. Alexandrowicz for useful discussions. EPSRC (EP/E004962/1) EPSRC (1363145

Portable lock-in amplifier for microcantilever based sensor array. Application to explosives detection using Co-BEA type zeolites as sensing materials

Recent advances in microcantilever-based sensors have led to a significant increase in sensitivity, making them a competitive solution in highly demanding applications as explosives detection. However, these sensors face severe challenges related to: reliability, sensitivity, reproducibility and throughput; that have yet to be solved for commercial applications. This paper describes our efforts in this direction, particularly on the reproducible detection of nitroaromatic type explosives by means of parallelization combined with: i) nanoporous solids as sensing materials; and, ii) a portable lowpower electronic readout interface capable of both excitation and measurement of the multisensing platform. The response of the sensor array, comprising 4 microcantilevers, due to presence of 2-nitrotoluene, a common explosive taggant, has been properly monitored. The obtained results with 4 identical Co-BEA coated Si microcantilevers underline the importance of a proper sensing material degassing on the sensor performance

Explosives detection by array of Si µ-cantilevers coated with titanosilicate type nanoporous materials

An array comprising 4 Si microcantilevers coated with nanoporous ETS-10 crystals sub-micrometric in size has been deployed as a multisensing platform for 2-nitrotoluene (an explosive related molecule) recognition. For such purposes, the adsorption properties of synthetic microporous ETS-10 titanosilicate type materials have been tailored by means of the Si/Ti ratio, and surface grafting with organic groups (amine, imidazol). Our general strategy for vapor detection of explosives involves the combination of Si based nanoporous solids as sensing materials and resonating Si cantilevers provided with self-heating elements as tiny microbalances (mass sensitivity factors ~18 Hz/ng). Particularly for this work, ETS-10 type titanosilicates with promoted basic properties (Si/Ti=4, -NH2 anchored on the external surface) exhibit the higher affinity towards nitroaromatic derivatives as electron defficient molecules. A high remarkable hydrophilic character is shown by titanosilicates modified by covalent linkage with imidazole based organosilane (above 17% wt. water uptake at room temperature). Accounting from such versatile sorption behavior, the family of nanoporous ETS-10 crystals has been deployed by microdropping technique over the 8 Si-microcantilevers chip. By means of a portable lowpower electronic interface capable of the simultaneous excitation and measurement of 4 sensor output signals, such multisensing platform has been successfully applied for 2-nitrotoluene detection at trace level

Explosives Detection by Array of Si µ -Cantilevers Coated with Titanosilicate-Type Nanoporous Materials

An array comprising four Si µ -cantilevers coated with nanoporous functionalized ETS-10 crystals sub-micrometric in size has been developed as a multisensing platform for explosives recognition in vapor phase. The detection capabilities of the proposed device have been tested for common taggants such as 1-methyl-2-nitro-benzene (o-MNT)] and explosives (commercial detonation cord, a plastic tube filled with pentaerythritol tetranitrate (PETN); and C-4, a mixture of cyclotrimethylenetrinitramine (RDX), binders and plastifiers). The general strategy for the detection of explosives in vapor phase is based on the characteristic fingerprint each one produces as a result of the dissimilar chemical interactions between the ETS-10 coated µ -cantilevers and the target molecules emanating from the explosives and swept by ambient air. A portable lock-in amplifier has been implemented to exploit the truly benefits of the array in terms of portability, reduced size, and energy consumption. Such low-power electronic interface is capable of creating the excitation signal as well as obtaining the response values of four resonating µ -cantilevers simultaneously. The resulting sensing platform has successfully been applied for the o-MNT, PETN, and RDX detection at trace level

Molecular diffusion on surfaces: The diffusive behavior of aromatic compounds absorbed on graphitic surfaces studied with Quasi-Elastic-Neutron Scattering (QENS)

Tesis Doctoral presentada por Irene Calvo Almazán en el Dpto. de Física de la Materia Condensada de la Universidad de Zaragoza.Este trabajo está dedicado al estudio de la dinámica de anillos aromáticos en fase adsorbida sobre el plano basal de microcristales de grafito, (es decir la familia de planos cuya dirección normal es paralela a la dirección [0001]). Se trata de un trabajo experimental basado en técnicas de dispersión quasi-elástica de neutrones. Hemos medido con técnicas espectroscópicas de tiempo de vuelo, la difusión de benceno hidrogenado, C6H6, para cuatro recubrimientos: desde 0.1 ML (sólo un 10 % de los sitios de adsorpción están ocupados), 0.2 ML, 0.5 ML y 1.0 ML (el 100 % de los sitios de adsorbción están ocupados) y la difusión de benceno deuterado, C6D6, para recubrimientos de 0.5 ML y 0.9 ML. Además hemos explorado un amplio rango de temperaturas: desde 60 K hasta 140 K, siendo la temperatura de desorpción del benceno en grafito de 150 K. Observamos que la dinámica de las moléculas es muy sensible al recubrimiento. A bajos recubrimientos (0.1ML) las moléculas cumplen un régimen balístico mientras que a medios y altos recubrimientos (a partir de 0.2 ML) la difusión es Browniana. Podemos extraer del análisis de los espectros la velocidad cuadrática promedia de las moléculas en régimen balístico y que satisfacen el principio de equipartición de la energía. En el caso de recubrimientos por encima de 0.2 ML hemos obtenido los parámetros de fricción del orden de 2.5±0.1 ps-1 (para 0.5 ML a 140K) y que es coherente con estudios recientes. Por otro lado, una estimación de la fricción fonónica en el plano basal del grafito conduce a un valor de 0.02 ps-1 que es al menos dos órdenes de magnitud menor que los parámetros de fricción extraídos de los ajuste de datos. Concluimos que la interacción entre adsorbatos gobierna el comportamiento difusivo de las moléculas mientras que la interacción entre adsorbatos y substrato juega un papel secundario.Peer reviewe

The application of quasi-elastic neutron scattering techniques (QENS) in surface diffusion studies

Neutron scattering techniques such as quasi-elastic neutron scattering, QENS, have proven to be well-suited tools for studying structure and dynamics of surface adsorbed molecules. In contrast to many more widely used surface science techniques neutron scattering allows the microscopic characterization of samples under a wide range of thermodynamic conditions, as the samples are not constrained to ultra high vacuum environment. Moreover, neutron scattering allows the separation of coherent and incoherent scattering, giving access to different diffusive mechanisms such as single particle diffusion, mass transport, rotations, or vibrations. In this paper we will review recent progress and the state-of-the-art in neutron scattering experiments on surface adsorbed molecules in the sub-monolayer coverage range with a specific emphasis on studies of carbon and other high surface density substrates. We will also cover recent progress in theoretical modeling, since the usefulness of neutron scattering data on surface dynamics can be strongly enhanced by computational modeling, such as molecular dynamics (MD) simulations and the development of analytical models

Impact and mitigation of angular uncertainties in Bragg coherent x-ray diffraction imaging

International audienceBragg coherent diffraction imaging (BCDI) is a powerful technique to explore the local strain state and morphology of microscale crystals. The method can potentially reach nanometer-scale spatial resolution thanks to the advances in synchrotron design that dramatically increase coherent flux. However, there are experimental bottlenecks that may limit the image reconstruction quality from future high signal-to-noise ratio measurements. In this work we show that angular uncertainty of the sample orientation with respect to a fixed incoming beam is one example of such a factor, and we present a method to mitigate the resulting artifacts. On the basis of an alternative formulation of the forward problem, we design a phase retrieval algorithm which enables the simultaneous reconstruction of the object and determination of the exact angular position corresponding to each diffraction pattern in the data set. We have tested the algorithm performance on simulated data for different degrees of angular uncertainty and signal-to-noise ratio

Ballistic Diffusion in Poly-aromatic Hydrocarbons on Graphite

This work presents an experimental picture of molecular ballistic diffusion on a surface, a process which is difficult to pinpoint since it generally occurs at very short length scales. By combining neutron-time-of-flight data, with molecular dynamics simulations and density functional theory calculations, we provide a complete description of the ballistic translations and rotations of a poly-aromatic hydrocarbon (PAH) adsorbed on the basal plane of graphite. Pyrene, C16H10, adsorbed on graphite is a unique system where at relative surface coverages of about 10-20 %, its mean free path matches the experimentally accessible time/space scale of neutron time-of-flight spectroscopy (IN6 at the Institut Laue-Langevin). The comparison between the diffusive behavior of large and small PAHs such as pyrene and benzene adsorbed on graphite, brings a strong experimental indication that the interaction between molecules is the dominating mechanism in the surface diffusion of poly-aromatic hydrocarbons adsorbed on graphite

General approaches for shear-correcting coordinate transformations in Bragg coherent diffraction imaging. Part II

International audienceX-ray Bragg coherent diffraction imaging (BCDI) has been demonstrated as a powerful 3D microscopy approach for the investigation of sub-micrometre-scale crystalline particles. The approach is based on the measurement of a series of coherent Bragg diffraction intensity patterns that are numerically inverted to retrieve an image of the spatial distribution of the relative phase and amplitude of the Bragg structure factor of the diffracting sample. This 3D information, which is collected through an angular rotation of the sample, is necessarily obtained in a non-orthogonal frame in Fourier space that must be eventually reconciled. To deal with this, the approach currently favored by practitioners (detailed in Part I) is to perform the entire inversion in conjugate non-orthogonal real- and Fourier-space frames, and to transform the 3D sample image into an orthogonal frame as a post-processing step for result analysis. In this article, which is a direct follow-up of Part I, two different transformation strategies are demonstrated, which enable the entire inversion procedure of the measured data set to be performed in an orthogonal frame. The new approaches described here build mathematical and numerical frameworks that apply to the cases of evenly and non-evenly sampled data along the direction of sample rotation (i.e. the rocking curve). The value of these methods is that they rely on the experimental geometry, and they incorporate significantly more information about that geometry into the design of the phase-retrieval Fourier transformation than the strategy presented in Part I. Two important outcomes are (1) that the resulting sample image is correctly interpreted in a shear-free frame and (2) physically realistic constraints of BCDI phase retrieval that are difficult to implement with current methods are easily incorporated. Computing scripts are also given to aid readers in the implementation of the proposed formalisms