Quantitative subsurface contact resonance force microscopy of model polymer nanocomposites.

We present experimental results on the use of quantitative contact resonance force microscopy (CR-FM) for mapping the planar location and depth of 50 nm diameter silica nanoparticles buried beneath polystyrene films 30-165 nm thick. The presence of shallowly buried nanoparticles, with stiffness greater than that of the surrounding matrix, is shown to locally affect the surface contact stiffness of a material for all depths investigated. To achieve the necessary stiffness sensitivity, the CR-FM measurements are obtained utilizing the fifth contact eigenmode. Stiffness contrast is found to increase rapidly with initial increases in force, but plateaus at higher loads. Over the explored depth range, stiffness contrast spans roughly one order of magnitude, suggesting good depth differentiation. Scatter in the stiffness contrast for single images reveals nonuniformities in the model samples that can be explained by particle size dispersity. Finite element analysis is used to simulate the significant effect particle size can have on contact stiffness contrast. Finally, we show how measurements at a range of forces may be used to deconvolve particle size effects from depth effects.

Gradient solvent vapor annealing of block copolymer thin films using a microfluidic mixing device.

Solvent vapor annealing (SVA) with solvent mixtures is a promising approach for controlling block copolymer thin film self-assembly. In this work, we present the design and fabrication of a solvent-resistant microfluidic mixing device to produce discrete SVA gradients in solvent composition and/or total solvent concentration. Using this device, we identified solvent composition dependent morphology transformations in poly(styrene-b-isoprene-b-styrene) films. This device enables faster and more robust exploration of SVA parameter space, providing insight into self-assembly phenomena.

Investigation of thermally responsive block copolymer thin film morphologies using gradients.

We report the use of a gradient library approach to characterize the structure and behavior of thin films of a thermally responsive block copolymer (BCP), poly(styrene-b-tert-butyl acrylate) (PS-b-PtBA), which exhibits chemical deprotection and morphological changes above a thermal threshold. Continuous gradients in temperature and film thickness, as well as discrete substrate chemistry conditions, were used to examine trends in deprotection, nanoscale morphology, and chemical structure. Thermal gradient annealing permitted the extraction of transformation rate constants (k(t)) for the completion of thermal deprotection and rearrangement of the film morphology from a single BCP library on hydroxyl and alkyl surfaces, respectively. The transformation rate constants ranged from 1.45 × 10(-4) s(-1) to 5.02 × 10(-5) s(-1) for temperatures between 185 and 140 °C for hydroxyl surfaces. For the same temperature range, the alkyl surfaces yielded k(t) values ranging from 4.76 × 10(-5) s(-1) to 5.73 × 10(-6) s(-1), an order of magnitude slower compared to hydroxyl surfaces. Activation energies of the thermal deprotection and film transformation on these surfaces were also extrapolated from linear fits to Arrhenius behavior. Moreover, we noted a morphology shift and orientation transformation from parallel lamellae to perpendicular cylinders at the free surface because of changes in volume fraction and surface energetics of the initially symmetric BCP. Using gradient techniques, we are able to correlate morphological and chemical structure changes in a rapid fashion, determine kinetics of transitions, and demonstrate the effect of surface chemistry on the deprotection reaction in thermally responsive BCP thin films.

Combinatorial mapping of substrate step edge effects on diblock copolymer thin film morphology and orientation.

We have used a combinatorial gradient technique to map precisely how the terrace structure and microdomain lattice alignment in a thin film of a sphere-forming diblock copolymer are affected by both the thickness of the copolymer film and the height of a series of parallel step edges fabricated on the substrate. We find that for film thicknesses slightly incommensurate with integer numbers of sphere layers, the step edges act as nucleation sites for regions with one more or one fewer layers of spheres. We also find that for our system, the hexagonal lattice formed by a single layer of spheres on the low side of a step edge is aligned along the direction of the step edge only where the film on the high side is sufficiently thin to support only a wetting layer of copolymer material. This work will guide the tuning of film thickness and step height in future studies and applications of graphoepitaxy in block copolymer films.

Effects of humidity and sample surface free energy on AFM probe-sample interactions and lateral force microscopy image contrast.

Contrast between hydrophilic and hydrophobic domains and probe-sample adhesion forces as a function of relative humidity (RH) and sample surface free energy have been investigated using hydrophilic and hydrophobic atomic force microscopy (AFM) probes. For hydrophobic probes, the adhesion force is low, and the AFM image contrast between hydrophilic and hydrophobic domains is poor over the 0-93% RH. For hydrophilic probes, the image contrast between the hydrophilic and hydrophobic domains is poor at low RH but improved at high RH. This image contrast change is related to adhesion force differences between the two domains. In turn, the enhanced adhesion and image contrasts at elevated RH are attributed to capillary forces, which are large over the hydrophilic domains but greatly diminished over the hydrophobic domains. The adhesion force increases slightly with sample surface free energy at low RH, but increases rapidly with increasing sample surface free energy at high RH. The results indicate that for AFM in air, tailoring the RH of the probe-sample environment and utilizing a hydrophilic probe can enhance imaging of materials chemical heterogeneity with nanoscale spatial resolution.

Quantifying residual stress in nanoscale thin polymer films via surface wrinkling.

Residual stress, a pervasive consequence of solid materials processing, is stress that remains in a material after external forces have been removed. In polymeric materials, residual stress results from processes, such as film formation, that force and then trap polymer chains into nonequilibrium stressed conformations. In solvent-cast films, which are central to a wide range of technologies, residual stress can cause detrimental effects, including microscopic defect formation and macroscopic dimensional changes. Since residual stress is difficult to measure accurately, particularly in nanoscale thin polymer films, it remains a challenge to understand and control. We present here a quantitative method of assessing residual stress in polymer thin films by monitoring the onset of strain-induced wrinkling instabilities. Using this approach, we show that thin (>100 nm) polystyrene films prepared via spin-coating possess residual stresses of approximately 30 MPa, close to the crazing and yield stress. In contrast to conventional stress measurement techniques such as wafer curvature, our technique has the resolution to measure residual stress in films as thin as 25 nm. Furthermore, we measure the dissipation of residual stress through two relaxation mechanisms: thermal annealing and plasticizer addition. In quantifying the amount of residual stress in these films, we find that the residual stress gradually decreases with increasing annealing time and plasticizer amounts. Our robust and simple route to measure residual stress adds a key component to the understanding of polymer thin film behavior and will enable identification of more effective processing routes that mitigate the detrimental effects of residual stress.

Living anionic polymerization using a microfluidic reactor.

Living anionic polymerizations were conducted within aluminum-polyimide microfluidic devices. Polymerizations of styrene in cyclohexane were carried out at various conditions, including elevated temperature (60 degrees C) and high monomer concentration (42%, by volume). The reactions were safely maintained at a controlled temperature at all points in the reactor. Conducting these reactions in a batch reactor results in uncontrolled heat generation with potentially dangerous rises in pressure. Moreover, the microfluidic nature of these devices allows for flexible 2D designing of the flow channel. Four flow designs were examined (straight, periodically pinched, obtuse zigzag, and acute zigzag channels). The ability to use the channel pattern to increase the level of mixing throughout the reactor was evaluated. When moderately high molecular mass polymers with increased viscosity were made, the patterned channels produced polymers with narrower PDI, indicating that passive mixing arising from the channel design is improving the reaction conditions.

Preparation of combinatorial arrays of polymer thin films for transmission electron microscopy analysis.

We present a new method for harvesting multiple thin film specimens from polymer combinatorial libraries for transmission electron microscopy (TEM) analysis. Such methods are of interest to researchers who wish to integrate TEM measurements into a combinatorial or high-throughput experimental workflow. Our technique employs poly(acrylic acid) plugs, sequestered in an elastomer gasket, to extract a series of film patches from gradient combinatorial libraries. A strategy for simultaneous deposition of the array of film specimens onto TEM grids also is described. We demonstrate our technique using nanostructured polymer thin film libraries as test cases in which the nanoscale details can be successfully imaged. Microscopy of test case specimens demonstrates that these samples are of sufficient quality for morphology screening via TEM, and in some cases are sufficient for more detailed morphological studies.

A microfluidic platform for integrated synthesis and dynamic light scattering measurement of block copolymer micelles.

Microfluidic devices were developed that integrate the synthesis of well defined block copolymers and dynamic light scattering (DLS) measurement of their micelle formation. These metal devices were designed to operate in contact with organic solvents and elevated temperatures for long periods, and thus were capable of continuous in-channel atom transfer radical polymerization (ATRP) of styrene and (meth)acrylate homopolymers and block copolymers. These devices were equipped with a miniaturized fiber optic DLS probe that included several technology improvements, including a measurement volume of only 4 microlitres, simple alignment, and reduced multiple scattering. To demonstrate the integrated measurement, poly(methyl methacrylate-b-lauryl methacrylate) and poly(methyl methacrylate-b-octadecyl methacrylate) block copolymers were processed on the device with a selective solvent, dodecane, to induce micelle formation. The in situ DLS measurements yielded the size and aggregation behavior of the micelles. For example, the block copolymer solutions formed discrete micelles (D(H) approximately = 25 nm) when the corona block was sufficiently long (f(MMA) < 0.51), but the micelles aggregated when this block was short. This study demonstrates the utility of these new devices for screening the solution behavior of custom synthesized polymeric surfactants and additives.

Versatile platform for creating gradient combinatorial libraries via modulated light exposure.

This article details the design, construction, and operation of flexible system that modulates light exposure for the purpose of fabricating continuous and discrete gradient combinatorial libraries. Designed for versatility, the device combines "off the shelf" components, modular accessories, and flexible computer control, so that it can be used for a variety of combinatorial research applications. Salient aspects and capabilities of the instrument are illustrated through two practical examples. The first case demonstrates how user defined exposure functions can be used to create continuous surface energy gradient libraries with a linear profile. The second example illustrates the creation of continuous and discrete libraries for mapping exposure-property functions in a photocurable polymer system.

Substrate surface energy dependent morphology and dewetting in an ABC triblock copolymer film.

A gradient combinatorial approach was used to examine the effect of substrate surface energy on the morphology and stability of films of a poly(isoprene-b-styrene-b-ethylene oxide) triblock copolymer that exhibits an alternating gyroid morphology in the bulk. Atomic force microscopy data across our surface energy (water contact angle) library suggest a transformation to predominantly surface parallel lamellae with an antisymmetric ordering. For substrate water contact angles below 70 degrees the film exhibited autophobic dewetting from an adsorbed half-period triblock copolymer monolayer at longer annealing times. X-ray photoelectron spectroscopy and near edge X-ray absorption fine structure analysis along gradient specimens indicated that the substrate surface energy governed the composition profile of the monolayer, and this variation in chemical expression was key to whether the film was stable or autophobically dewet. These observations demonstrate that enthalpic interactions, in addition to entropic considerations, can play a major role in autophobic dewetting of block copolymer films.

Pattern-directed to isotropic dewetting transition in polymer films on micropatterned surfaces with differential surface energy contrast.

Surface chemical patterns can both cause and direct dewetting in overlying thin polymer films. In this paper we focus on a key factor in this phenomenon, the magnitude of the surface energy difference between surface pattern domains (Δ). To probe the influence of Δ on film dewetting, we utilize novel combinatorial test patterns exhibiting a gradient in Δ. Specifically, our test patterns consist of a series of micron-scale striped regions that continuously change in their surface energy () relative to background striped regions having a fixed and calibrated . Using polystyrene (PS) films as a demonstration case, we employ these test patterns to quantify the morphology and kinetics of dewetting as Δ diminishes. Our study indicates a transition from pattern-directed to isotropic PS dewetting at critical Δ values. For Δ > 14 mJ m, ordered droplet arrays are formed, while for Δ < 7 mJ m, the dewetting is isotropic. A competition between these limiting behaviors is found for a "crossover regime", 7 mJ m < Δ < 14 mJ m. These combinatorial test patterns provide a powerful approach for investigating the large number of parameters that govern the stability of ultrathin polymer films, and the physical factors that influence the dewetted film morphology.

Gradient chemical micro patterns: a reference substrate for surface nanometrology.

We present fabrication routes for a new type of surface specimen that exhibits a micro pattern with a gradient in chemical contrast between the pattern domains. Design elements in the specimen allow chemical contrast in the micro pattern to be related to well-established surface characterization data, such as contact angle measurements. These gradient specimens represent a reference tool for calibrating image contrast in chemically sensitive scanning probe microscopy techniques and a platform for the high-throughput analysis of polymer thin film behavior.

Monolayer formation of PBLG-PEO block copolymers at the air-water interface.

Physicochemical properties of PBLG (poly(gamma-benzyl-l-glutamate))-PEO (poly(ethylene oxide)) diblock copolymers composed of PBLG as the hydrophobic rod component and PEO as the hydrophilic component were investigated at the air-water interface. Surface pressure-area isotherms obtained by the Wilhelmy plate method provide several variables such as molecular size, compressibility of PEO, and the free energy change of the PBLG-PEO block copolymer. GE-1 (M(w) of PBLG:PEO=103,700:12,000), with a relatively longer rod, has negative temperature effects and GE-3 (M(w) of PBLG:PEO=8400:12,000), with a relatively shorter rod, shows a positive temperature effect because of the large entropy loss. These competitions were based on the block size of PBLG and PEO and were affected by various microstructures of the PBLG-PEO diblock copolymer. Monolayer aggregations transferred onto mica from the air-water interface were analyzed with AFM. AFM images of GE-1 monolayers show cylindrical micelles, but the self-assembled structure has many large domains. The monolayer of GE-2 (M(w) of PBLG:PEO=39,800:12,000), which has a medium size rod, forms a spherical structure at the air-water interface. Monolayers of GE-3, with a short rod length, form bilayer structures. These results demonstrate that the microstructures of PBLG-PEO diblock copolymers are related to free energy changes between rod and coil blocks.

Fourier analysis near-field polarimetry for measurement of local optical properties of thin films.

We present measurements of the local diattenuation and retardance of thin-film specimens by using techniques that combine near-field scanning optical microscopy (NSOM) and a novel polarization-modulation (PM) polarimetry utilizing Fourier analysis of the detected intensity signal. Generally, quantitative near-field polarimetry is hampered by the optical anisotropy of NSOM probes. For example, widely used aluminum-coated pulled-fiber aperture probes typically exhibit a diattenuation near 10%. Our analysis of aperture diattenuation demonstrates that the usual techniques for nulling a PM polarimeter result in a nonzero residual probe retardance in the presence of a diattenuating tip. However, we show that both diattenuation and retardance of the sample can be determined if the corresponding tip properties are explicitly measured and accounted for in the data. In addition, in thin films (<100 nm thick), where the sample retardance and diattenuation are often small, we show how to determine these polarimetric quantities without requiring alignment of the fast and diattenuating axes, which is a more general case than has been previously discussed. We demonstrate our techniques by using two types of polymer-film specimens: ultrahigh molecular weight block copolymers (recently noted for their photonic activity) and isotactic polystyrene spherulites. Finally, we discuss how changes in the tip diattenuation during data collection can limit the accuracy of near-field polarimetry and what steps can be taken to improve these techniques.