D. K. Satapathy

Diffractive imaging for periodic samples: retrieving one-dimensional concentration profiles across microfluidic channels

A technique has been developed that allows determination of the concentration profiles of colloidal solutions or any kind of fluid under confinement. Currently, submicrometre-wide channels are sampled with a resolution in the 10 nm range. The method comprises regular arrays of microfluidic channels and one-dimensional X-ray phase-retrieval techniques for the analysis of small-angle X-ray diffraction from the array structures. Recording the X-ray diffraction data requires a low dose on each individual channel since the sum of the signals from all channels is detected. The determined concentration profiles represent the ensemble average rather than individual entities and are obtained in a model-independent way. As an example, amplitude and phase of the exit field and concentration profiles for a colloidal fluid within confining channels of different widths are shown.

Magnetic proximity effect in YBa2Cu3O7 / La2/3Ca1/3MnO3 and YBa2Cu3O7 / LaMnO3+δ superlattices

Using neutron reflectometry and resonant x-ray techniques we studied the magnetic proximity effect (MPE) in superlattices composed of superconducting YBa2Cu3O7 and ferromagnetic-metallic La0.67Ca0.33MnO3 or ferromagnetic-insulating LaMnO(3+δ). We find that the MPE strongly depends on the electronic state of the manganite layers, being pronounced for the ferromagnetic-metallic La0.67Ca0.33MnO3 and almost absent for ferromagnetic-insulating LaMnO(3+δ). We also detail the change of the magnetic depth profile due to the MPE and provide evidence for its intrinsic nature.

Confinement-induced orientational alignment of quasi-2D fluids

We have developed a unique approach for studying the ensemble-averaged nearest-neighbor coordination of confined fluids by combining small-angle X-ray scattering and phase-retrieval–based X-ray diffraction from fluid-filled nanofluidic channel arrays. We apply the method to a charge-stabilized quasi–two-dimensional colloidal fluid (particle diameter 48 nm), focusing on the structural transition from a monolayer to a bilayer with increasing fluid film thickness. In contrast to theoretical work on the paradigmatic hard-sphere fluid, we find unambiguous experimental evidence for orientational alignment of fluids in extreme confinement.

In situ characterization of block copolymer ordering on chemically nanopatterned surfaces by time-resolved small angle x-ray scattering

The assembly of lamella-forming block copolymer blend thin films on chemically nanopatterned striped surfaces was monitored in real time with small angle x-ray scattering (SAXS) in transmission mode. The strongest diffraction from the assembled grating structure was detected after 4.5min of annealing as the temperature was ramped from 100to240°C at a rate of about 20°C∕min. Real-space images were also obtained from samples annealed for specific times using top-down scanning electron microscopy (SEM) and this identified structures formed during annealing that are unique to the block copolymer blends. The data are compared to previously reported SEM and molecular simulation studies with pure block copolymers. Because it can be used in real time and probes the entire film thickness, transmission SAXS proved to be a useful tool for better understanding the block copolymer annealing process.

Depht Profile of the ferromagnetic order in a YBa2Cu3O7/La2/3Ca1/3MnO3 superlattice on a LSAT Substrate :A polarized Neutron reflectometry study

Using polarized neutron reflectometry (PNR) we have investigated a YBa2Cu3O7(10nm)/La2/3Ca1/3MnO3(9nm)]10 (YBCO/LCMO) superlattice grown by pulsed laser deposition on a La0.3Sr0.7Al0.65Ta0.35O3 (LSAT) substrate. Due to the high structural quality of the superlattice and the substrate, the specular reflectivity signal extends with a high signal-to-background ratio beyond the fourth order superlattice Bragg peak. This allows us to obtain more detailed and reliable information about the magnetic depth profile than in previous PNR studies on similar superlattices that were partially impeded by problems related to the low temperature structural transitions of the SrTiO3 substrates. In agreement with the previous reports, our PNR data reveal a strong magnetic proximity effect showing that the depth profile of the magnetic potential differs significantly from the one of the nuclear potential that is given by the YBCO and LCMO layer thickness. We present fits of the PNR data using different simple block-like models for which either a ferromagnetic moment is induced on the YBCO side of the interfaces or the ferromagnetic order is suppressed on the LCMO side. We show that a good agreement with the PNR data and with the average magnetization as obtained from dc magnetization data can only be obtained with the latter model where a so-called depleted layer with a strongly suppressed ferromagnetic moment develops on the LCMO side of the interfaces. The models with an induced ferromagnetic moment on the YBCO side fail to reproduce the details of the higher order superlattice Bragg peaks and yield a wrong magnitude of the average magnetization. We also show that the PNR data are still consistent with the small, ferromagnetic Cu moment of 0.25muB that was previously identified with x-ray magnetic circular dichroism and x-ray resonant magnetic reflectometry measurements on the same superlattice.

Buckling and layering transitions in confined colloids

We report layering transitions within a charged silica colloidal dispersion confined by two opposite like-charged dielectric walls. The ensemble- averaged concentration profiles of the colloids (radius 60 +/- 2 nm) along the confinement direction have been determined using synchrotron X-ray diffraction from microfluidic arrays of channels of different widths. For small channel widths up to a critical value of 300 nm, the channel can accommodate just one layer of colloids which is stabilized against buckling by the confining charged walls. For channel widths larger than this critical value, a buckling of the single layer is observed. These phenomena are explained using a theoretical analysis of buckling instabilities due to Chou and Nelson, and a value for the charge density on the stabilizing charged walls is derived. At still larger channel widths a sequence of complex layering transitions is observed which involve the splitting and merging of individual layers. Copyright (C) EPLA, 2009

Mechanism and dynamics of block copolymer directed assembly with density multiplication on chemically patterned surfaces

In this work, we used scanning electron microscopy (SEM), in situ coherent small angle x-ray scattering (SAXS), and Monte Carlo molecular simulation to gain insights into the dynamics of block copolymer directed assembly with density multiplication on chemically patterned surfaces. During directed assembly, it was observed with SEM that poly(styrene-block-methyl methacrylate) initially formed discrete polystyrene domains that lacked long-range order at the free surface. After further annealing, the polystyrene domains gradually coalesced into linear domains that were not registered fully with the underlying chemical pattern. The linear domains could be trapped in metastable morphologies. Finally, the linear polystyrene domains formed perpendicular lamellae in full registration with the underlying chemical pattern. It was revealed with SAXS that scattering peaks characteristic of the period of the chemical pattern appeared and disappeared at the early stages of assembly. Finally, the morphological evolutio...

Molecular liquid under nanometre confinement: density profiles underlying oscillatory forces

Ultrathin (<12 nm) films of tetrakis(trimethyl)siloxysilane (TTMSS) have been confined by atomically flat mica membranes in the presence and absence of applied normal forces. When applying normal forces, discrete film thickness transitions occur, each involving the expulsion of TTMSS molecules. Using optical interferometry we have measured the step size associated with a film thickness transition (7.5 Å for compressed, 8.4 Å for equilibrated films) to be smaller than the molecular diameter of 9.0 Å. Layering transitions with a discrete step size are commonly regarded as evidence for strong layering of the liquids molecules in planes parallel to the confining surfaces and it is assumed that the layer spacing equals the measured periodicity of the oscillatory force profile. Using x-ray reflectivity (XRR), which directly yields the liquids density profile along the confinement direction, we show that the layer spacing (10-11 Å) proves to be on average significantly larger than both the step size of a layering transition and the molecular diameter. We observe at least one boundary layer of different electron density and periodicity than the layers away from the surfaces.

Azimuthal reflection high-energy electron diffraction study of MnAs growth on GaAs(001) by molecular beam epitaxy

Azimuthal reflection high-energy electron diffraction (ARHEED) and in situ grazing incidence synchrotron x-ray diffraction techniques are employed to investigate the growth, epitaxial orientation, and interfacial structure of MnAs layers grown on GaAs(001) by molecular beam epitaxy (MBE). We demonstrate the power and reliability of ARHEED scans as a routine tool in characterizing the formation of epitaxial films. The ARHEED scans clearly reveal the formation of the rectangular MnAs unit cell during growth on GaAs(001) for a MnAs layer thickness of 2.1 ± 0.2 monolayers with a tensile strain along the MnAs[112−0] direction. A periodic coincidence site lattice, which is known to form along the MnAs [0001] direction to release the strain due to the huge lattice mismatch (∼30%) also produces periodic satellites of the diffraction spots in the ARHEED scan. The formation of different epitaxial orientations of MnAs during MBE growth can be directly observed using ARHEED scans. ARHEED is demonstrated to have a resolution similar to synchrotron x-ray diffraction with a double crystal monochromator, yielding full width at half maximum values of reflections as small as 0.005 reciprocal lattice units.Azimuthal reflection high-energy electron diffraction (ARHEED) and in situ grazing incidence synchrotron x-ray diffraction techniques are employed to investigate the growth, epitaxial orientation, and interfacial structure of MnAs layers grown on GaAs(001) by molecular beam epitaxy (MBE). We demonstrate the power and reliability of ARHEED scans as a routine tool in characterizing the formation of epitaxial films. The ARHEED scans clearly reveal the formation of the rectangular MnAs unit cell during growth on GaAs(001) for a MnAs layer thickness of 2.1 ± 0.2 monolayers with a tensile strain along the MnAs[112−0] direction. A periodic coincidence site lattice, which is known to form along the MnAs [0001] direction to release the strain due to the huge lattice mismatch (∼30%) also produces periodic satellites of the diffraction spots in the ARHEED scan. The formation of different epitaxial orientations of MnAs during MBE growth can be directly observed using ARHEED scans. ARHEED is demonstrated to have a res...

X-ray reflectivity theory for determining the density profile of a liquid under nanometre confinement

The determination of out-of-plane density profiles of a confined molecular liquid by synchrotron X-ray reflectivity is presented.