Synchrotron Grazing Incidence X-ray Research Articles

Morphologies of Self-Organizing Regioregular Conjugated Polymer/Fullerene Aggregates in Thin Film Solar Cells

In this study, we used simultaneous synchrotron grazing incidence X-ray scattering and diffraction to elucidate the overall morphologies of bulk heterojunction (BHJ) thin film (ca. 100 nm) solar cells containing phase-separated poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) domains. Specifically, the dimensions and orientation of the P3HT crystallites and the sizes of the PCBM aggregates in BHJ thin films were determined. The appropriate PCBM aggregate size and density required for an optimum performance of the film in the photovoltaics device resulted in deteriorated ordering in the out-of-plane direction, but improved the in-plane packing of the P3HT lamellae. When the P3HT crystallites and PCBM aggregates had comparable domain sizes and number densities, the interpercolated networks for electron- and hole-transport were optimized in the film. This new understanding of the underlying mechanism of carrier mobility in BHJ thin films might be crucial in improving the efficiency of future solar cells.

Structural Transitions in Polydiacetylene Langmuir Films

Polydiacetylene (PDA) Langmuir films (LFs) were investigated directly at the air/water interface using in situ synchrotron grazing incidence X-ray diffraction, and ex situ transmissison electron microscopy and diffraction. The films were compressed and polymerized on pure water. A crystallographic model describes the structures and phase transitions of the unpolymerized (monomer) film, via the metastable (blue phase), to the fully stable PDA red phase as a function of irradiation dose. The monomer-to-blue-to-red chromatic phase transitions are accompanied by changes in the in-plane crystal structure and pendant chains packing arrangement from arced alkyl chains (in the monomer and blue phases) to near-vertical closely packed chains in the red phase. Notably, the characteristic linear strand morphology of PDA films can be explained as a direct result of the marked decrease in spacing between adjacent polymer chains upon transition from the blue to the red phase.

Biomineralization of a Self-Assembled Extracellular Matrix for Bone Tissue Engineering

Understanding how biomineralization occurs in the extracellular matrix (ECM) of bone cells is crucial to the understanding of bone formation and the development of a successfully engineered bone tissue scaffold. It is still unclear how ECM mechanical properties affect protein-mineral interactions in early stages of bone mineralization. We investigated the longitudinal mineralization properties of MC3T3-E1 cells and the elastic modulus of their ECM using shear modulation force microscopy, synchrotron grazing incidence X-ray diffraction (GIXD), scanning electron microscopy, energy dispersive X-ray spectroscopy, and confocal laser scanning microscopy (CLSM). The elastic modulus of the ECM fibers underwent significant changes for the mineralizing cells, which were not observed in the nonmineralizing cells. On substrates conducive to ECM network production, the elastic modulus of mineralizing cells increased at time points corresponding to mineral production, whereas that of the nonmineralizing cells did not vary over time. The presence of hydroxyapatite in mineralizing cells and the absence thereof in the nonmineralizing ones were confirmed by GIXD, and CLSM showed that a restructuring of actin occurred only for mineral-producing cells. These results show that the correct and complete development of the ECM network is required for osteoblasts to mineralize. This in turn requires a suitably prepared synthetic substrate for bone development to succeed in vitro.

Impact of interfacial polymer morphology on photoexcitation dynamics and device performance in P3HT/ZnO heterojunctions

To understand the critical factor(s) that influence short-circuit current in poly(3-hexylthiophene) (P3HT)/ZnO solar cells, we investigate the morphology of the interfacial polymer layer and the photoexcitation dynamics in the picosecond regime. Thin (∼6 nm) films of P3HT deposited on bare ZnO and ZnO modified with an alkanethiol monolayer are used as model systems for the heterojunction interface. Results are compared with thin P3HT films on glass for the behavior of the polymer alone. Synchrotron grazing incidence X-ray diffraction spectra of P3HT thin films deposited on glass and on an alkanethiol-modified ZnO surface identify a crystalline P3HT interfacial layer, while an amorphous interfacial layer of P3HT is found on unmodified ZnO. To investigate the decay dynamics of initial photoexcited states, the samples are interrogated by pump–probe spectroscopy with sub-picosecond time resolution. Compared to P3HT/ZnO composite films, the decay behavior for both polarons and excitons over a 500 ps time interval becomes significantly slower with alkanethiol modification, indicating a reduction in early-stage charge recombination. These experiments demonstrate how the interfacial polymer morphology has a critical role in determining device performance.

Phase Transitions in Thin Films of a Diblock Copolymer Composed of a Linear Polymer Block and a Brush Polymer Block with Mesogenic Oligothiophenyl Bristles

In this study, we quantitatively investigated the temperature-dependent phase transition behaviors in thin films of an interesting semirod−coil diblock copolymer, poly(styrene)-b-poly(oligothiophene side chain modified isoprene) (PS-b-POTI), and the resulting morphological structures using synchrotron grazing incidence X-ray scattering combined with differential scanning calorimetry. These analyses provided detailed information about the morphologies of the phase-separated domains and the molecular structures formed in each domain. At room temperature, the diblock copolymer molecules in thin films were found to form an alternately stacked structure comprised of amorphous PS and smectic-A POTI microdomains whose stacking direction is parallel to the film plane. On heating, the films underwent a phase transformation to a hexagonal cylinder structure with cylindrical POTI domains in the PS matrix oriented normal to the film plane. This phase conversion is induced by the transformation of the POTI domains fro...

Integration of Ganglioside GT 1b Receptor into DPPE and DPPC Phospholipid Monolayers: An X-Ray Reflectivity and Grazing-Incidence Diffraction Study

Using synchrotron grazing-incidence x-ray diffraction (GIXD) and reflectivity, the in-plane and out-of-plane structures of mixed-ganglioside GT 1b-phospholipid monolayers were investigated at the air-liquid interface and compared with monolayers of the pure components. The receptor GT 1b is involved in the binding of lectins and toxins, including botulinum neurotoxin, to cell membranes. Monolayers composed of 20 mol % ganglioside GT 1b, the phospholipid dipalmitoyl phosphatidylethanolamine (DPPE), and the phospholipid dipalmitoyl phosphatidylcholine (DPPC) were studied in the gel phase at 23°C and at surface pressures of 20 and 40 mN/m, and at pH 7.4 and 5. Under these conditions, the two components did not phase-separate, and no evidence of domain formation was observed. The x-ray scattering measurements revealed that GT 1b was intercalated within the host DPPE/DPPC monolayers, and slightly expanded DPPE but condensed the DPPC matrix. The oligosaccharide headgroups extended normally from the monolayer surfaces into the subphase. This study demonstrated that these monolayers can serve as platforms for investigating toxin membrane binding and penetration.

Order−Order and Order−Disorder Transitions in Thin Films of an Amphiphilic Liquid Crystalline Diblock Copolymer

In this study, we quantitatively investigated the temperature-dependent phase transition behaviors of thin films of an interesting amphiphilic diblock copolymer, poly(ethylene oxide)-b-poly(11-[4-(4-butylphenylazo)phenoxy]undecyl methacrylate) (p(EO)-b-p(MAAZ)) and the resulting morphological structures by using synchrotron grazing incidence X-ray scattering (GIXS) and differential scanning calorimetry. The quantitative GIXS analysis showed that the diblock copolymer in the homogeneous, isotropic melt state undergoes phase-separation near 190 degrees C and then forms a body-centered cubic (BCC) structure of spherical p(EO) domains in the p(MAAZ) matrix, at which point the p(EO) domains and the p(MAAZ) matrix are both in amorphous, liquid states. The BCC structure of spherical p(EO) domains is converted to a hexagonal cylinder structure near 120 degrees C, which is induced by the transformation of the isotropic phase of the p(MAAZ) matrix to the smectic A phase, which is composed of a laterally ordered structure of p(MAAZ) blocks with fully extended side groups. The resulting hexagonal cylinder structure is very stable below 120 degrees C. This microscopic hexagonal cylinder structure is retained as the smectic A phase of the p(MAAZ) matrix undergoes further transitions to smectic C near 104 degrees C and to a smectic X phase near 76 degrees C, while the amorphous, liquid phase of the p(EO) cylinders undergoes crystallization near -15 degrees C. These complicated temperature-dependent disorder-order and order-order phase transitions in the films were found to take place reversibly during the heating run. A face-centered orthorhombic structure of p(EO) domains was also found during the heating run and is an intermediate structure in the hexagonal cylinder structure to BCC structure transformation. We use these structural analysis results to propose molecular structure models at various temperatures for thin films of the diblock polymer.

Detailed analysis of gyroid structures in diblock copolymer thin films with synchrotron grazing-incidence X-ray scattering

In this study, a grazing-incidence X-ray scattering (GIXS) formula was derived for gyroid structures formed in thin films supported on substrates. Two-dimensional GIXS patterns were measured for gyroid structures formed in polystyrene-b-polyisoprene (PS-b-PI) diblock copolymer nanometre-scale thin films supported on silicon substrates, and a quantitative analysis of the obtained two-dimensional GIXS data was conducted with the scattering formula. This analysis provided details (lattice parameter, width of the PS phase, positional distortion factor, orientation and orientation distribution) of the gyroid structures developed in the diblock copolymer thin films that are not easily obtained using conventional techniques. Moreover, it was possible to simulate complete and detailed two-dimensional GIXS patterns with the determined structure parameters.

Quantitative analysis of lamellar structures in brush polymer thin films by synchrotron grazing-incidence X-ray scattering

In this study, a grazing-incidence X-ray scattering (GIXS) formula was derived for lamellar structures formed in thin films supported on substrates, and a comprehensive numerical analysis was performed using the scattering formula. A quantitative analysis was conducted of lamellar structures formed in nanometre-scaled thin films of a brush polymer, poly[oxy(n-decylthiomethylenyl)ethylene], supported on silicon substrates, by GIXS measurements during cooling and subsequent heating, and data analysis was performed using the scattering formula. This analysis provided details (long period, sub-layers and their thicknesses, volume fraction, bristle paracrystal distortion factor, and orientation) of the lamellar structure with varying temperature that are not easily obtained using conventional techniques. Moreover, a molecular structure model and electron density profiles were established.

Nondestructive quantitative synchrotron grazing incidence X-ray scattering analysis of cylindrical nanostructures in supported thin films

Nondestructive nanostructural analysis is indispensable in the development of nanomaterials and nanofabrication processes for use in nanotechnology applications. This paper demonstrates a quantitative, nondestructive analysis of nanostructured thin films supported on substrates and their templated nanopores by using grazing incidence X-ray scattering and data analysis with a derived scattering theory. The analysis disclosed that vertically oriented nanodomain cylinders had formed in 20–100 nm thick films supported on substrates, which consisted of a mixture of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) and PMMA homopolymer, and that the PMMA nanodomain cylinders were selectively etched out by ultraviolet light exposure and a subsequent rinse with acetic acid, resulting in a well ordered nanostructure consisting of hexagonally packed cylindrical nanopores.

Quantitative analysis of molecularly stacked layer structures in supported organic thin films by synchrotron grazing-incidence X-ray scattering

In this study, we derive a grazing-incidence X-ray scattering (GIXS) formula to analyze quantitatively GIXS patterns for molecularly stacked layer structures in substrate-supported nanoscale thin films. We apply this formula in the quantitative analysis of GIXS patterns obtained for S-docosanylcysteine thin films on silicon substrates with native oxide layers. This analysis successfully provides information on the structural parameters and orientation of the molecular layer stack developed in S-docosanylcysteine thin films.

Structural analysis of thin films of novel polynorbornene derivatives by grazing incidence X-ray scattering and specular X-ray reflectivity along with ellipsometry

In the present study, structural analyses using synchrotron grazing incidence X-ray scattering, specular reflectivity and ellipsometry were performed on thin films of two novel polynorbornene derivatives, chiral poly(norbornene acid methyl ester) and racemic poly(norbornene acid n-butyl ester), which are potential low dielectric constant materials for advanced microelectronic and display applications. These analyses provided important information on the structure, electron density gradient across the film thickness, chain orientation, refractive index and thermal expansion characteristics of the polymers in substrate-supported thin films. The structural characteristics and properties of the thin films depended on the tacticity of the polymer chain and were further influenced by the film thickness and thermal annealing history.

Indium adsorption on GaN under metal-organic chemical vapor deposition conditions

Real-time synchrotron grazing-incidence x-ray fluorescence is employed to study indium adsorption on the GaN (0001) surface under typical process conditions for InGaN metal-organic chemical vapor deposition. An indium condensation boundary is mapped as a function of trimethylindium pressure, substrate temperature, and carrier gas composition. Below the condensation boundary, indium surface coverage reaches a maximum of ∼1∕4 ML. The addition of 8% H2 to the carrier gas is found to have a significant effect on both condensation and adsorption of indium.

Synchrotron x-ray scattering study of thin epitaxial Pr2O3 films on Si(001)

We investigate the structural and interfacial properties of thin Pr2O3 films on Si(001) substrates grown by molecular beam epitaxy using synchrotron grazing incidence x-ray diffraction and reflectivity measurements in ultrahigh vacuum. The epitaxial films consist of two orthogonal [101]-oriented cubic domains, with equal proportion. The average in-plane domain sizes are larger than the film thickness. Scans along crystal truncation rods confirm the cubic Mn2O3 structure of the epitaxial layer. A small amount of hexagonal Pr2O3 is found in thin films. Its fraction increases with increasing layer thickness indicating that it is not confined to the interface. Reflectivity measurements reveal an additional layer at the Pr2O3∕Si(001) interface, which is extended by in situ annealing. Transmission electron microscopy of the samples confirms the structural properties of the films found by the x-ray measurements and shows that the interfacial layers are nonuniform with a coexistence of crystalline and amorphous regions.

Microstructure and Chemistry of Annealed Al–Cu–Fe–Cr Quasicrystalline Approximant Coatings

An as-deposited Al–Cu–Fe–Cr film was annealed in flowing argon to study development of a quasicrystalline approximant microstructure. Sputter profile x-ray photoemission spectroscopy analysis showed oxygen incorporation reached approximately 70 at.% at the surface of the film, declined monotonically, and stabilized at ∼10 at.% at a depth of 160 nm. Synchrotron grazing incidence x-ray scattering was used to probe the structure of the coating at various penetration depths by altering the angle of the incident x-ray beam. An amorphous structure was observed near the termination surface, which coexisted with a compressively strained crystalline aluminum. These phases were the dominant microstructure to a depth of 110 nm. Below 150 nm, the film was primarily O1 decagonal approximant. Cross-section transmission electron microscopy elucidated a columnar growth morphology with associated porosity in the interstices between the columns. The resulting development of the Al–Cu–Fe–Cr decagonal approximant coatings from the precursor is reported.

Adaptive chemistry of bifunctional gold nanoparticles at the air/water interface. A synchrotron X-ray study of giant amphiphiles.

A series of ligand stabilized gold nanoparticles with diameters close to 3 nm were studied as Langmuir monolayers at the air/water interface by synchrotron X-ray diffraction and reflectivity. Alkylthiols with different length and/or terminal functional group (hydrophilic or hydrophobic) were introduced into the ligand shell by ligand place exchange reactions. Synchrotron grazing incidence X-ray diffraction (GIXD) and specular X-ray reflectivity reveal the well known hexagonally packed monolayers. In addition the mixed hydrophilic/hydrophobic ligand shell nanoparticles show a high degree of environmental responsiveness, as they adapt to an amphiphilic distribution of ligands around the gold core when spread at the water surface. Likewise nanoparticles of mixed long and short alkyl chains respond to lateral pressure by adopting a structure where the short alkyl chains determine the in-plane nearest neighbor distance while the long alkyl chains determine the film thickness. Based on X-ray reflectivity measurements, which quantitatively account for the electron density in the monolayers, combined with GIXD we calculate the average size and number of atoms of the individual gold particle cores, and estimate the number of passivating ligand on the particle surface. Typical values are dAU-core = 16 A, dnanoparticle = 26-37 A depending on the ligands, Mw = 30-40000 g mol(-1) number of ligands = 40-60. The thickness of the monolayers was determined by AFM after transfer of the monolayers to a solid support using the Langmuir Schaefer technique. The combination of the different techniques produce a very consistent picture of the structure and adaptive chemical nature of the nanoparticles studied, and reveal a surprisingly monodisperse particle distribution centered around 140 atoms in the gold core.

GIXRD of nanoscale strain patterning in wafer bonding

Synchrotron grazing incidence X-ray diffraction is used to study tuneable lateral dislocation superlattices obtained by Si wafer bonding. Deformation satellites peaks around the {2 2 0 } reflections are measure for pure twist and mixed (twist–tilt) grain boundaries. The twist of the two crystals induces a square network of screw dislocations whose features are calculated by continuum elasticity theory and kinematical approximation. The tilt of the crystals is accommodated by alternated mixed dislocations and the interactions between these two networks is discussed from the X-ray diffraction measurements.

Lipid discrimination in phospholipid monolayers by the antimicrobial frog skin peptide PGLa. A synchrotron X-ray grazing incidence and reflectivity study.

We present a first study using synchrotron grazing incidence diffraction and X-ray reflectivity measurements on mixed phospholipid/peptide monolayers at the air/water interface. The thermodynamic properties of the pure and mixed monolayers were characterized using the classical film balance technique. Surface pressure/potential-area isotherms showed that the antimicrobial frog skin peptide PGLa formed a very stable monolayer with two PGLa molecules per kinetic unit and a collapse pressure of ~22 mN/m. X-ray grazing incidence diffraction indicated that the peptide-dimer formation did not lead to self-aggregation with subsequent crystallite formation. However, the scattering length density profiles derived from X-ray reflectivity measurements yield information on the PGLa monolayer that protrudes into the air phase by about 0.8 nm, suggesting that the peptide is aligned parallel to the air/water interface. The monolayers, composed of disaturated phosphatidylcholines or phosphatidylglycerols, were stable up to 60 mN/m and exhibited a first-order transition from a liquid-expanded to a liquid-condensed state around 10 mN/m. Structural details of the phospholipid monolayers in the presence and absence of PGLa were obtained from synchrotron experiments. Thereby, the X-ray data of distearoylphosphatidylcholine/PGLa can be analyzed by being composed of the individual components, while the peptide strongly perturbed the lipid acyl chain order of distearoylphosphatidylglycerol. These results are in agreement that PGLa mixes at a molecular level with negatively charged lipids, but forms separate islands in zwitterionic phosphatidylcholine monolayers and demonstrates that antimicrobial peptides can discriminate between the major phospholipid components of bacterial and mammalian cytoplasmic membranes.

Influence of palmitic acid and hexadecanol on the phase transition temperature and molecular packing of dipalmitoylphosphatidyl-choline monolayers at the air–water interface

Palmitic acid (PA) and 1-hexadecanol (HD) strongly affect the phase transition temperature and molecular packing of dipalmitoylphosphatidylcholine (DPPC) monolayers at the air–water interface. The phase behavior and morphology of mixed DPPC/PA as well as DPPC/HD monolayers were determined by pressure-area-isotherms and fluorescence microscopy. The molecular organization was probed by synchrotron grazing incidence x-ray diffraction using a liquid surface diffractometer. Addition of PA or HD to DPPC monolayers increases the temperature of the liquid-expanded to condensed phase transition. X-ray diffraction shows that DPPC forms mixed crystals both with PA and HD over a wide range of mixing ratios. At a surface pressure (π) of 40 mN/m, increasing the amount of the single chain surfactant leads to a reduction in tilt angle of the aliphatic chains from nearly 30° for pure DPPC to almost 0° in a 1:1 molar ratio of DPPC and PA or HD. At this composition we also find closest packing of the aliphatic chains. Further increase of the amount of PA or HD does not change the lattice or the tilt.

Packing of Ganglioside-Phospholipid Monolayers: An X-Ray Diffraction and Reflectivity Study

Using synchrotron grazing-incidence x-ray diffraction (GIXD) and reflectivity, the in-plane and out-of-plane structure of mixed ganglioside-phospholipid monolayers was investigated at the air-water interface. Mixed monolayers of 0, 5, 10, 20, and 100 mol% ganglioside GM 1 and the phospholipid dipalmitoylphosphatidylethanolamine (DPPE) were studied in the solid phase at 23°C and a surface pressure of 45 mN/m. At these concentrations and conditions the two components do not phase-separate and no evidence for domain formation was observed. X-ray scattering measurements reveal that GM 1 is accommodated within the host DPPE monolayer and does not distort the hexagonal in-plane unit cell or out-of-plane two-dimensional (2-D) packing compared with a pure DPPE monolayer. The oligosaccharide headgroups were found to extend normally from the monolayer surface, and the incorporation of these glycolipids into DPPE monolayers did not affect hydrocarbon tail packing (fluidization or condensation of the hydrocarbon region). This is in contrast to previous investigations of lipopolymer-lipid mixtures, where the packing structure of phospholipid monolayers was greatly altered by the inclusion of lipids bearing hydrophilic polymer groups. Indeed, the lack of packing disruptions by the oligosaccharide groups indicates that protein-GM 1 interactions, including binding, insertion, chain fluidization, and domain formation (lipid rafts), can be studied in 2-D monolayers using scattering techniques.