Grazing incidence small-angle X-ray scattering: an advanced scattering technique for the investigation of nanostructured polymer films

Hamburg workshop on the "application of synchrotron radiation in chemistry"With grazing incidence small-angle X-ray scattering (GISAXS) the limitations of conventional small-angle X-ray scattering with respect to extremely small sample volumes in the thin-film geometry are overcome. GISAXS turned out to be a powerful advanced scattering technique for the investigation of nanostructured polymer films. Similar to atomic force microscopy (AFM), a large interval of length between molecular and mesoscopic scales is detectable with a surface-sensitive scattering method. While with AFM only surface topographies are accessible, with GISAXS the buried structure is also probed. Because a larger surface area is probed, GISAXS also has a much larger statistical significance compared to AFM. Due to the high demand on collimation, GISAXS experiments are based on synchrotron radiation. Nanostructures parallel and perpendicular to the sample surface observable in thin poly(styrene- block-isoprene) diblock copolymer films are presented as an example of the possibilities of GISAXS.     

Comparative analysis of nanostructured diblock copolymer films

Nanostructured polymer films of poly(styrene-block-paramethylstyrene) diblock copolymers P(Sd-b-pMS) on silicon substrates with a native oxide layer are investigated. Resulting from a storage under toluene vapor, a surface structure is installed. The early stages, characterized by the creation of a host structure out of an initially continuous film, are addressed. Grazing incidence small-angle X-ray scattering (GISAXS) experiments were performed as a function of exposure time. Results are compared to modelling of the scattering pattern and other experimental techniques, such as grazing incidence small-angle neutron scattering (GISANS) and atomic force microscopy (AFM) data. Possibilities and limits of the techniques are discussed.     

Time-resolved ultrathin cobalt film growth on a colloidal polymer template

Cobalt (Co) sputter deposition onto a colloidal polymer template is investigated using grazing incidence small-angle X-ray scattering (GISAXS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). SEM and AFM data picture the sample topography, GISAXS the surface and near-surface film structure. A two-phase model is proposed to describe the time evolution of the Co growth. The presence of the colloidal template results in the correlated deposition of an ultrathin Co film on the sample surface and thus in the creation of Co capped polystyrene (PS) colloids. Well below the percolation threshold, the radial growth is restricted and only height growth is observed.     

The effect of vacuum-ultraviolet laser wavelengths on the surface treatment of polyolefinic polymers

The laser-induced modification of the surface morphology of poly(propylene) fibers and films was investigated. It is known that strongly absorbing fibers such as poly(ethylene terephthalate) and polyamide obtain characteristic surface morphologies after treatment with 193 or 248 nm laser irradiation. Polyolefinic material cannot be modified directly (i.e., without doping) by irradiation with these wavelengths. Therefore experiments were carried out using a 157 nm F₂-laser. After irradiation in a vacuum chamber at fluences in excess of 50 mJ/cm² poly(propylene) also reveals the well-known surface morphology. Compared with aromatic polymers a rather high number of pulses is needed to generate the effect. © 1993 John Wiley & Sons, Inc.     

Quantitative SAXS analysis of oriented 2D hexagonal cylindrical silica mesostructures in thin films obtained from nonionic surfactants

Oriented mesostructured surfactant-silica nanocomposite thin films with a 2D hexagonal mesostructure of cylindrical micelles were prepared by evaporation-induced self-assembly using two different nonionic Brij surfactants and studied by small-angle X-ray scattering in symmetric reflection (SRSAXS) and grazing incidence (GISAXS) geometries. A novel SRSAXS evaluation approach was applied that allowed a good fitting of the SRSAXS data over almost the whole range of scattering vectors. Aside from the cylinder radius and the lattice parameter, the approach provided accurate values for the polydispersity of the micelles, lattice distortions, and preferred orientation. These analyses revealed a significant rise of the micelle radius and accordingly the lattice parameter upon an increase in the ratio surfactant/SiO(2), attributable to a decrease in the solubilization of the poly(ethylene oxide) (PEO) chains by water, in agreement with Monte Carlo simulations. Furthermore, the SRSAXS analysis was successfully applied to the corresponding mesoporous films for the determination of pore sizes.     

In situ GISAXS investigation of gold sputtering onto a polymer template

Microphase-separation structures in mixed diblock-triblock copolymer thin films are used for the incorporation of gold atoms inside the polymer matrix via sputtering of gold. Polystyrene (PS) spheres are arranged in a liquidlike type with a well defined nearest neighbor distance inside a polyisoprene matrix acting as a template for directing the gold atoms. Sputtering conditions are selected with a very low sputtering rate to avoid clustering in the atmosphere so that gold reaches the polymer surface in its atomic state. Due to the mobility of the gold atoms and the selective interaction with the PS parts of the microphase separation structure, gold is accumulated inside the polymer film in the PS spheres, as probed in situ with grazing incidence small-angle X-ray scattering (GISAXS). Nominally 4.3 A of gold is deposited, which by diffusion is spread out vertically over a thickness of 280 nm. UV-vis spectroscopy reveals a small blue shift for the gold sputtered polymer film. Atomic force microscopy proves the absence of gold clusters on the film surface. For low sputtering rate, GISAXS proves good sensitivity for gold migration inside the polymer film and opens new possibilities for studying polymer-metal interaction.     

Surface versus confinement induced morphology transition in triblock copolymer films: a grazing incidence small angle neutron scattering investigation

The internal nanostructure resulting from microphase separation in triblock copolymer films of polyparamethylstyrene-block-polystyrene-block-polyparamethylstyrene, P(pMS-b-Sd8-b-pMS), has been investigated with grazing incidence small angle neutron scattering (GISANS). X-ray reflectivity, grazing incidence small-angle X-ray scattering (GISAXS), optical microscopy and atomic force microscopy (AFM) complement the investigation. The influence of two limiting interfaces present in confinement is compared to the presence of only one surface. GISANS allows for the detection of structures in the very limited sample volume of confined films as well as for a depth sensitivity to probe the near free surface part of bulk films. With respect to the surface a perpendicular oriented lamella is observed. In contrast to the shrinkage of the characteristic lamellar spacing in confinement at the free surface, a slight increase is determined.     

Simulation and interpretation of 2D diffraction patterns from self-assembled nanostructured films at arbitrary angles of incidence: from grazing incidence (above the critical angle) to transmission perpendicular to the substrate

A method to calculate the location of all Bragg diffraction peaks from nanostructured thin films for arbitrary angles of incidence from just above the critical angle to transmission perpendicular to the film is reported. At grazing angles, the positions are calculated using the distorted wave Born approximation (DWBA), whereas for larger angles where the diffracted beams are transmitted though the substrate, the Born approximation (BA) is used. This method has been incorporated into simulation code (called NANOCELL) and may be used to overlay simulated spot patterns directly onto two-dimensional (2D) grazing angle of incidence small-angle X-ray scattering (GISAXS) patterns and 2D SAXS patterns. The GISAXS simulations are limited to the case where the angle of incidence is greater than the critical angle (alpha(i) > alpha(c)) and the diffraction occurs above the critical angle (alpha(f) > alpha(c)). For cases of surfactant self-assembled films, the limitations are not restrictive because, typically, the critical angle is around 0.2 degrees but the largest d spacings occur around 0.8 degrees 2theta. For these materials, one finds that the DWBA predicts that the spot positions from the transmitted main beam deviate only slightly from the BA and only for diffraction peaks close the critical angle. Additional diffraction peaks from the reflected main beam are observed in GISAXS geometry but are much less intense. Using these simulations, 2D spot patterns may be used to identify space group, identify the orientation, and quantitatively fit the lattice constants for SAXS data from any angle of incidence. Characteristic patterns for 2D GISAXS and 2D low-angle transmission SAXS patterns are generated for the most common thin film structures, and as a result, GISAXS and SAXS patterns that were previously difficult to interpret are now relatively straightforward. The simulation code (NANOCELL) is written in Mathematica and is available from the author upon request.     

Long-Range Lateral Correlation between Self-Assembled Domains of Fluorocarbon-Hydrocarbon Tetrablocks by Quantitative GISAXS

The structure and lateral correlation of fluorocarbon-hydrocarbon tetrablock di(F10Hm) domains at the air/water interface have been determined by quantitative analysis of grazing incidence small-angle X-ray scattering (GISAXS) data. The measured GISAXS signals can be well represented by the full calculation of the form and structure factors. The form factor suggests that di(F10Hm) domains take a hemiellipsoid shape. Both major and minor axes of the hemiellipsoids monotonically increased in response to the elongation of the hydrocarbon blocks, which can be explained by the concominant increase in van der Waals interaction. The structure factor calculated from the GISAXS signals suggests that the domains take an orthorhombic lattice. Remarkably, the lateral correlation can reach over a distance that is more than 14 times longer than the distance to the nearest neighbors. Our data suggest that quantitative GISAXS enables the optimal design of mesoscopic self-assemblies at the air/water interface by fine-tuning of the structures of molecular building blocks.     

Influence of polymer molecular weight on the chemical modifications induced by UV laser ablation

This paper investigates the influence of polymer molecular weight (M(W)) on the chemical modifications of poly(methyl methacrylate), PMMA, and polystyrene, PS, films doped with iodonaphthalene (NapI) and iodophenanthrene (PhenI), following irradiation at 248 nm (KrF excimer laser, 20 ns fwhm and hybrid excimer-dye laser, 500 fs fwhm) and at 308 nm (XeCl excimer laser, 30 ns fwhm). The changes of intensity and position of the polymer Raman bands upon irradiation provide information on cleavage of the polymer bonds. Degradation of PMMA, which is a weak absorbing system at 248 nm, occurs to a higher extent in the case of a larger M(W), giving rise to the creation of unsaturation centers and to degradation products. For highly absorbing PS, no degradation is observed upon irradiation with a KrF laser. Consistently irradiating doped PS at 308 nm, where the absorption is low, induces degradation of the polymer. Results provide direct support for the bulk photothermal model, according to which ejection requires a critical number of broken bonds. In the case of irradiation of doped PMMA with pulses of 248 nm and 500 fs, neither degradation nor dependence with polymer M(W) are observed, indicating that mechanisms involved in the femtosecond laser ablation differ from those operating in the case of nanosecond laser ablation. Participation of multiphoton/avalanche processes is proposed.     

Morphology of poly(lactide)-block-poly(dimethylsiloxane)-block-polylactide high-χ triblock copolymer film studied by grazing incidence small-angle X-ray scattering

The morphologies of poly(lactide)-block-poly(dimethylsiloxane)-block-polylactide (PLA-b-PDMS-b-PLA) triblock copolymer films were studied using a combination of grazing-incidence small-angle X-ray scattering, X-ray reflectivity and scanning electron microscopy. This block copolymer is characterized by a high Flory–Huggins interaction parameter which leads to the self-assembly of periodic high-resolution nanodomains. In this article, we performed a detailed analysis of GISAXS patterns, in the frame of the Distorted Wave Born Approximation, in order to determine the morphology of blocks and their spatial arrangement. For a low volume fraction of PLA (17%), a three-dimensional hexagonal lattice of PLA spherical blocks is revealed, while, for a PLA fraction twice larger, in-plane (parallel) PLA lying cylinders adopt a two-dimensional centered rectangular lattice. Moreover, the in-depth electron density profile of the polymer film for the cylindrical morphology was extracted from the XRR data, revealing the presence of interfacial layers at the top surface and at the interface with the Si substrate.     

Alkaline-solution-induced crystallization in poly(butylene terephthalate)

Subtle crystalline structure changes of poly(butylene terephthalate) (PBT) specimens treated with an alkali solution at room temperature were investigated with the grazing incidence X-ray diffraction (GIXRD) analysis method. A new phenomenon was found: the aqueous alkali solution induced the crystallization of the PBT polymer. Under the GIXRD analysis condition of an incidence angle of 1°, the penetration depth of the X-ray in PBT was less than 80 μm, and this agreed well with the rough theoretical estimation. The alkali solution adopted in this study was an aqueous sodium hydroxide solution, which had a concentration of 2.5 N. Dissolved quantities of the surface layers during the alkaline treatment were found to be small. No appreciable intrinsic viscosity change due to the alkaline treatment was detected. Possible factors that might contribute to the crystallization, such as water absorption and a chemical reagent effect, were examined, and a plausible explanation for the phenomenon was developed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1938–1948, 2004     

Stacking of main chain-crown ether polymers in thin films

Thin films (9-70 nm) of a series of polymers containing in the main chain dibenzo-18-crown-6 ether unit (DB18C6) linked to an aliphatic spacer of different length (10C and 14C) and nature have been prepared, from chloroform solutions, by spin coating on a silicon substrate. The quality and homogeneity of the polymer coatings was revealed by their reflectivity spectra and atomic force microscopy (AFM). The grazing incidence small-angle X-ray scattering (GISAXS) patterns show an out-of-plane structure correlation (interference maximum near the horizon) of scale size related to the polymer repeating unit length. Above this Bragg reflection, the shape of the scattering observed, in the GISAXS pattern, reveals an orientation of the stacked molecular columns in the coated polymer. A thermal treatment of the samples improves the nanostructure by increasing the lamellar coherence size (in y-direction) as well as the vertical orientation of the molecular columns.     

Microbeam grazing incidence small angle X-ray scattering—a new method to investigate heterogeneous thin films and multilayers

The combination of the ID13/ESRF micrometer-sized X-ray beam with the reflection geometry allowed to establish a new scattering method for investigating laterally patterned heterogeneous multilayers and interfaces. This new method—called microbeam grazing incidence small angle X-ray scattering (μGISAXS)—has been applied to a novel gradient multilayer of self-assembled nanometer-sized noble metal clusters on top of a polymer layer, being of significant importance for many technological applications, including biorecognitive sensoring. The new feature of using a 5 μm X-ray beam allows to characterize laterally heterogeneous samples on two length scales, induced by the small beamsize and reciprocal space resolution. From the two-dimensional μGISAXS patterns the three-dimensional structure and morphology of the gradient of gold (Au) clusters was reconstructed using detailed model simulations. Though being a highly complex sample, it turned out that the gradient is characterized by a single parameter, namely the cluster height. Atomic force microscopy (AFM) and optical absorption spectra provide supplementary information and help to enlighten the structure of evaporated gold clusters on polymer layers.     

Effect of different types of radiation on the composition of poly(phosphazene) surface

Changes in the composition of poly[bis(trifluoroethoxy)phosphazene] surface irradiated at ?? = 6700 Å (a laser), at ?? = 9.89 Å (1253.6 eV, X-ray Mg-K?? radiation), and at 4720 Å (a light emitting diode, (LED) for medical applications) were studied in situ by X-ray photoelectron spectroscopy. Both quantitative and qualitative changes in the surface composition compared to routine measurements of the polymer spectra are observed during an analysis of the surface upon long-term X-ray irradiation or with an increase in the X-ray radiation source power. These are the changes in the concentrations of elements and the appearance of additional states of carbon, oxygen, and nitrogen atoms. The composition of the surface irradiated with the laser and LED remains unchanged.     

Effect of interfacial interaction on the cross-sectional morphology of tobacco mosaic virus using GISAXS

We have investigated the effect of the interfacial interaction on the cross-sectional morphology of the tobacco mosaic virus (TMV) in solution and on two types of solid substrates, SiOx (polar) on Si(100) and polystyrene film (nonpolar) on Si(100), using small-angle X-ray scattering (SAXS) and grazing incidence small-angle X-ray scattering (GISAXS), respectively. Results reveal that the flexible chains at the outer surface of TMV either expand or contract depending on the nature of the substrate. Although the unfavorable interaction between the TMV and the PS causes a minimal effect, the stronger attractive interaction between the outer protein surface of TMV and the SiOx substrate induces pronounced deformation of its cross-sectional morphology.     

Layer-by-layer fabrication of an anatase titania multilayer with gradual sponge-like morphology

The fabrication of a functional multilayer system with a gradually hierarchical order formed by individual titania thin films of different porosity is investigated. The porous or sponge-like nanostructures are fabricated using a diblock copolymer assisted sol–gel process. The successive spin-coating of the sol–gel solution onto the silicon substrate deposits a thin polymer nanocomposite film which is transformed to purely anatase titania nanostructures via calcination. In total, this procedure is repeated layer by layer for three times. This layer-by-layer approach is monitored with grazing incidence small-angle X-ray scattering (GISAXS) after each fabrication step. The GISAXS investigation is complemented in real space with a scanning electron microscopy characterization of the respective preparation stages. From the characterization, a porous titania multilayer system with gradually structured levels is clearly identified.     

Reversible Morphology Control in Block Copolymer Films via Solvent Vapor Processing: An In Situ GISAXS study

The real time changes occurring within films of cylinder-forming poly(α-methylstyrene-block-4-hydroxystyrene) (PαMS-b-PHOST) were monitored as they were swollen in tetrahydrofuran (THF) and acetone solvent vapors. In situ information was obtained by combining grazing incidence small angle X-ray scattering (GISAXS) with film thickness monitoring of the solvent vapor swollen films. We show that for self assembly to occur, the polymer thin film must surpass a swollen thickness ratio of 212% of its original thickness when swollen in THF vapors and a ratio of 268% for acetone vapor annealing. As the polymer becomes plasticized by solvent vapor uptake, the polymer chains must become sufficiently mobile to self assemble, or reorganize, at room temperature. Using vapors of a solvent selective to one of the blocks, in our case PHOST-selective acetone, an order-order transition occured driven by the shift in volume fraction. The BCC spherical phase assumed in the highly swollen state can be quenched by rapid drying. Upon treatment with vapor of a non-selective solvent, THF, the film maintained the cylindrical morphology suggested by its dry-state volume fraction. In situ studies indicate that self-assembly occurs spontaneously upon attaining the threshold swelling ratios.     

Surface characterization of laser-treated poly(ethylene terephthalate) by optical profilometry and scanning tunneling microscopy

Characteristic changes in the surface topography due to UV laser treatment are of high significance for the determination of material destruction thresholds and surface structure development. E.g. irradiation of poly(ethylene terephthalate) (PET) film with pulsed UV laser light of 248 nm modifies the smoth surface of the polymer into a well oriented structured surface. The development of these structures were studied with scanning tunneling microscopy (STM) and high resolution optical profilometry. Three dimensional data of the surface were taken from the samples after each laser pulse. A change of topographic data was found in relation to fluence and number of pulses applied. © 1993 John Wilcy & Sons, Inc.