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We investigated the segmental dynamics of asymmetrically confined polymer films and report an unusual phenomenon in which the presence and thickness of a soft confining layer are responsible for significant changes in the segmental dynamics of the confined films. Specifically, the segmental dynamics of poly(vinyl alcohol) (PVA) thin films asymmetrically confined between hard aluminum (Al), and soft polystyrene (PS) films are shown to shift by as much as half an order of magnitude upon changes in the thicknesses of the confining PS layer. These effects are more significant than those due to symmetric confinement between hard Al substrates or exposure to a free surface. These observations, partially rationalized in terms of recent simulations and theory, implicate the role of the moduli of the confining layers.

We show evidence of thickness-dependent elastic mechanical moduli that are associated largely with the effects of architecture (topology) and the overall shape of the macromolecule. Atomic force microscopy (AFM) based nanoindentation experiments were performed on linear chain polystyrene (LPS) and star-shaped polystyrene (SPS) macromolecules of varying functionalities (number of arms, f) and molecular weights per arm Mwarm. The out-of-plane elastic moduli E(h) increased with decreasing film thickness, h, for h less than a threshold film thickness, hth. For SPS with f ≤ 64 and Mwarm > 9 kg/mol, the dependencies of E(h) on h were virtually identical for the linear chains. Notably, however, for SPS with f = 64 and Mwarm = 9 kg/mol (SPS-9k-64), the hth was over 50% larger than that of the other polymers. These observations are rationalized in terms of the structure of the polymer for high f and sufficiently small Mwarm and not in terms of the influence of interfacial interactions.

In thin film A/B polymer/polymer mixtures, the formation of a layer at the free surface, with average composition that differs from the bulk, due to the preferential segregation of the lower cohesive energy density component, is well understood. While much is also understood about this surface layer formation and growth to date, virtually nothing is known about the surface dynamics of the chains in such mixtures. Questions about the surface chain dynamics in relation to the bulk have remained unanswered. With the use of X-ray photon correlation spectroscopy (XPCS) we show that the dynamics of poly(vinyl methyl ether) (PVME) chains at the free surface of polystyrene (PS)/PVME thin film mixtures can be orders of magnitude larger than the PVME chains in the bulk. These dynamics manifest from differences between the local compositions of the blend at the free surface and the bulk, as well as film thickness constraints.

The performance of conjugated polymer (CP)-based electronic devices relies on optimal charge carrier mobilities, which are determined by monomeric architecture, degree of polymerization, chain conformation, and the nano- and mesoscale morphologies. With regard to the latter, we discuss two effects that have received limited attention in the literature, yet important for device performance optimization: (1) the role of morphological disorder and of CP/substrate interactions on the in-plane and out-of-plane carrier transport in CPs; (2) the impact of morphological disorder on charge transfer at the CP/substrate interface. The emergence of film thickness-dependent carrier mobilities, varying over two orders of magnitude within a length scale of 200 nm, and band-bending phenomena, extending tens of nanometers within the CP, are associated with these effects. These findings suggest areas for further research in order to enable widespread applications of next-generation CP-based devices. Graphical abstract

Upon quenching a polymer melt to a temperature T below its glass transition temperature Tg, structural relaxations, physical aging, enable the material to return to equilibrium. Whereas the physica...

The transport of charge carriers throughout an active conjugated polymer (CP) host, characterized by a heterogeneous morphology of locally varying degrees of order and disorder, profoundly influences the performance of CP-based electronic devices, including diodes, photovoltaics, sensors, and supercapacitors. Out-of-plane charge carrier mobilities (μout-of-plane) across the bulk of the active material host and in-plane mobilities (μin-plane) parallel to a substrate are highly sensitive to local morphological features along their migration pathways. In general, the magnitudes of μout-of-plane and μin-plane are very different, in part because these carriers experience different morphological environments along their migration pathways. Suppressing the impact of variations in the morphological order/disorder on carrier migration remains an important challenge. While much is known about μin-plane and its optimization for devices, the current challenges are associated with μout-of-plane and its optimization for device performance. Therefore, this review is devoted to strategies for improving μout-of-plane in neat CP films and the implications for more complex systems, such as D:A blends which are relevant to OPV devices. The specific strategies discussed for improving μout-of-plane include solvent/field processing methods, chemical modification, thickness confinement, chemical additives, and different post-annealing strategies, including annealing with supercritical fluids. This review leverages the most recent fundamental understanding of mechanisms of charge transport and connections to morphology, identifying robust design strategies for targeted improvements of μout-of-plane.

In situ, real-time polarized Raman spectroscopy was used to measure electrostatically induced carbon nanotube alignment in a polymer matrix. Discrete and reversible asymptotes of carbon nanotube G-band intensity were observed as a function of the applied electric field strength. It is proposed that as the electric field is increased, certain populations of carbon nanotubes attain sufficient alignment energy to overcome the randomizing thermal energy of the system. This is attributed to the electrostatic torque being a function of nanotube length, a relation that has been shown for dielectric rods and is extended here to carbon nanotubes. Nanotube batches of varying length distributions (hundreds of nanometers to micron-length) were created with different amounts of sonication energy. These distributions were quantified with atomic force microscopy measurements, and a model was developed relating these length distributions to the change in nanotube alignment at various electric field strengths. Nanotube polarizabilities determined from the model ( α = 10 − 30 − 10 − 32 F ⋅ m 2 ) were consistent with previously reported values. The effects of processing parameters such as sonication on the degree of achievable alignment as well as its implications are also discussed.

Spatial compositional heterogeneity strongly influences the dynamics of the A and B components of bulk miscible blends. Its effects are especially apparent in mixtures, such as poly(vinyl methyl ether) (PVME)/polystyrene (PS), where there exist significant disparities between the component glass transition temperatures (Tgs) and relaxation times. The relaxation processes characterized by distinct temperature dependencies and relaxation rates manifest different local compositional environments for temperatures above and below the glass transition temperature of the miscible blend. This same behavior is shown to exist in miscible PS/PVME films as thin as 100 nm. Moreover, in thin films, the characteristic segmental relaxation times τ of the PVME component of miscible PVME/PS blends confined between aluminum (Al) substrates decrease with increasing molecular weight M of the PS component. These relaxation rates are film thickness dependent, in films up to a few hundred nanometers in thickness. This is in rema...

Viscoelastic properties are central for gels and other materials. Simultaneously, high storage and loss moduli are difficult to attain due to their contrarian requirements to chemical structure. Biomimetic inorganic nanoparticles offer a promising toolbox for multiscale engineering of gel mechanics, but a conceptual framework for their molecular, nanoscale, mesoscale, and microscale engineering as viscoelastic materials is absent. Here we show nanoparticle gels with simultaneously high storage and loss moduli from CdTe nanoparticles. Viscoelastic figure of merit reaches 1.83 MPa exceeding that of comparable gels by 100–1000 times for glutathione-stabilized nanoparticles. The gels made from the smallest nanoparticles display the highest stiffness, which was attributed to the drastic change of GSH configurations when nanoparticles decrease in size. A computational model accounting for the difference in nanoparticle interactions for variable GSH configurations describes the unusual trends of nanoparticle gel viscoelasticity. These observations are generalizable to other NP gels interconnected by supramolecular interactions and lead to materials with high-load bearing abilities and energy dissipation needed for multiple technologies., Achieving simultaneous high storage and loss moduli in gels is difficult due to the opposite chemical structure requirements needed for such properties. Here the authors show a spectrum of gels containing CdTe nanoparticles stabilized by glutathione that have such properties which can be rationalised through the developed model.

Incorporating nanoparticles (NPs) within a polymer host to create polymer nanocomposites (PNCs) while having the effect of increasing the functionality (e.g., sensing, energy conversion) of these materials influences other properties. One challenge is to understand the effects of nanoparticles on the viscosity of nanoscale thick polymer films. A new mechanism that contributes to an enhancement of the viscosity of nanoscale thick polymer/nanoparticle films is identified. We show that while the viscosities of neat homopolymer poly(2-vinylpyridine) (P2VP) films as thin as 50 nm remained the same as the bulk, polymer/nanoparticle films containing P2VP brush-coated gold NPs, spaced 50 nm apart, exhibited unprecedented increases in viscosities of over an order of magnitude. For thicker films or more widely separated NPs, the chain dynamics and viscosities were comparable to the bulk values. These results—NP proximities and suppression of their dynamics—suggest a new mechanism by which the viscosities of polymer...

The segmental relaxation times τA and τB of the A and B components, respectively, of an A/B polymer/polymer blend typically exhibit dissimilar temperature dependences and can differ by orders of magnitude, thereby manifesting the influence of spatial compositional heterogeneity. We show that for weakly miscible A/B blends the relaxations of the faster A component occur via separate and distinct mechanisms. In the melt state, τA increases in a nonlinear manner as temperature T decreases toward blend glass transition temperature Tg(blend) (or toward the local effective glass transition temperature of its component Tg(A)); this is the typical α relaxation process. For temperatures below the transition, 1/τA exhibits an Arrhenius temperature dependence; this is identified as the α′ process. A third relaxation process, a so-called α0 process, also occurs in the melt state; it is slower than the α process and exhibits a significantly stronger dependence on temperature. Each relaxation process, characterized by ...

Structural relaxations of a substance quenched to a temperature Tage below its glass transition temperature Tg enable the structure of the substance to approach equilibrium. This phenomenon, also known as physical aging, has been studied for many decades in bulk linear-chain polymer systems, where the aging rates are generally, to first order, independent of chain length. More recently, the phenomenon has been of keen interest in thin films, where the aging rate is shown to be film thickness H dependent, for films in the thickness range of nanometers to a few hundred nanometers. We show here, based on a study of polystyrene star-shaped polymers of a wide range of functionalities 2 ≤ f ≤ 64 and arm molecular weights Marm, that in the limit of sufficiently large values of Marm the aging behavior is similar to that of linear chains—independent of Marm and f. More importantly, in the limit of sufficiently small Marm and large f, the aging rate is independent of film thickness. Otherwise, the rate is a nonmono...

The potential for polymer thin films to be used as coatings or dielectrics is limited by their low thermal conductivity, κ. However, there have been very limited studies on κ enhancement for polymer thin films. In this work, we show that the out-of-plane κ of a poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) thin film can be enhanced when it undergoes the appropriate thermal annealing conditions. When the film is annealed above its melting temperature, we achieve a 300–400% increase in κ across the measured temperature range, compared to the as-cast film. We attribute this enhancement to the extensive ordering of polymer backbone chains perpendicular to the substrate during the melt-recrystallization process.

The performance of power conversion devices is impacted by the energy level alignment at the interface between the conjugated polymer and conductive substrate. While band bending has been known to vary between conjugated polymers, we show that the degree of band bending within the same polymer can be just as significant with morphology change. Specifically, a significant band bending effect, studied via Kelvin probe force microscopy (KPFM), was exhibited by poly(3-hexylthiophene) (P3HT) films fabricated using matrix assisted pulsed laser evaporation (MAPLE) in contrast to the conventional spin-cast P3HT films. This finding is associated with a broadening of the density of states (DOS) in the MAPLE-deposited P3HT films, originating from the more disordered structure of the film. These findings, to the best of our knowledge, illustrate for the first time a strong connection between morphology, energy level alignment, and bulk transport in conjugated polymer films.

The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. The MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π–π stacking, and conjugated backbone directions. Moreover, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. Despite the seemingly unfavorable molecular orientations and the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 vs. 54 meV) to those reported in the literature for high mobility polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 39–48

We investigated the phase behavior of thin film, thickness h ≈ 100 nm, mixtures of a polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer with star-shaped polystyrene (SPS) molecules of varying functionalities f, where 4 ≤ f ≤ 64, and molecular weights per arm Marm. The miscibility of the system and the surface composition varied appreciably with Marm and f. For large values of Marm, regardless of f, the miscibility of the system was qualitatively similar to that of linear chain PS/PS-b-P2VP mixtures – the copolymer chains aggregate to form micelles, each composed of an inner P2VP core and PS corona, which preferentially segregate to the free surface. On the other hand, for large f and small Marm, SPS molecules preferentially resided at the free surface. Moreover, blends containing SPS molecules with the highest values of f and lowest values of Marm were phase separated. These observations are rationalized in terms of competing entropic interactions and the dependence of the surface tension of the star-shaped molecules on Marm and f.

Thin films of the conjugated polymer poly(3-hexylthiophene) (P3HT) of different morphological structures were fabricated using both conventional spin-casting and the matrix-assisted pulsed laser evaporation (MAPLE). Films deposited by MAPLE exhibit inhomogeneous morphologies comprised globular subfeatures with dimensions of the order of 100 nm. We show that whereas the in-plane carrier mobilities of MAPLE-deposited films (8.3 × 10−3 cm2/V/s) are comparable with those of spin-cast analogs (5.5×10−3 cm2/V/s), the out-of-plane mobilities are an order of magnitude lower (4.1 × 10−4cm2/V/s versus 2.7 × 10−3 cm2/V/s). Both in- and out-of-plane carrier transport characteristics of MAPLE-deposited films indicate a broad density of states and high carrier trap concentration. Optical absorbance spectroscopy not only corroborates a high degree of energetic disorder in MAPLE-deposited films, but also suggests that the P3HT chains possess average conjugation lengths comparable with spin-cast counterparts. Our findings, rationalized in terms of the Gaussian Disorder Model, describing carrier transport in an environment characterized by both positional and energetic disorder, provide important perspectives on the extent to which disorder impacts mechanisms of charge transport in conjugated polymers.

The role of self-assembled monolayers (SAMs), trichloro(1 H,1 H,2 H,2 H-perfluorooctyl) (FTS) and octadecyltrichlorosilane (OTS), deposited on indium tin oxide (ITO) substrates, on electronic properties of the poly(3-hexylthiophene) (P3HT)/SAM/ITO system is reported. SAMs, well known for modifying the surface energies of materials, are also known to modify the work functions (WFs) of semiconductors. Unsurprisingly, differences between the band-bending behaviors of P3HT/ITO, P3HT/OTS/ITO, and P3HT/FTS/ITO systems were observed because the SAMs modify the WF of ITO. However, the degrees of band bending occurring in these systems could not be attributed solely to the modified WFs of the substrate. This was apparent based on measurements of samples that included P3HT films prepared with different morphological structures. Changes in the morphological structure, due to different deposition methods and surface energies of the substrates, are necessarily connected to changes in the electronic structure, including changes in the electronic density of states (DOS), of P3HT. An association between (i) the WF differences between P3HT, ITO, and SAM/ITO substrates, (ii) the surface energies of the ITO and SAM/ITO substrates, which influence the morphology of the deposited P3HT layer, (iii) the DOS widths of P3HT, and (iv) the degree of band bending is suggested.

Traditional organolead-halide perovskite-based devices have shown rapid improvements in their power conversion efficiency in less than a decade, yet challenges remain for improving stability and film uniformity, as well as the elimination of lead to address toxicity issues. We fabricated lead-free methylammonium bismuth iodide (MBI) perovskite films and studied the effect of solvent annealing with dimethylformamide (DMF) on both (1) the crystallinity and structure of the films with X-ray diffraction and scanning electron microscopy and (2) the local optoelectronic properties of the films as measured via (photo)conductive atomic force microscopy. We found that solvent annealing leads to improved crystallinity and increased grain size in the MBI films as compared to the thermally annealed films. Furthermore, solvent-annealed MBI films show significantly increased electrical conductivity in the out-of-plane direction. Photoconductivity in both solvent-annealed and thermally annealed MBI films was increased in the grain interiors versus the grain boundaries. It was observed that DMF-induced solvent annealing impacts charge transport through the film, which can be a unique design parameter for optimizing local optoelectronic properties. By studying how solvent annealing affects the MBI film structure and changes the ways in which charges are transported through the film, we have developed a better understanding of how local optoelectronic properties are affected by DMF annealing.

Applications of polymer thin films include functional coatings, flexible electronics, membranes and energy conversion. The physical properties of polymer films of nanoscale thicknesses typically differ from the bulk, due largely to entropic effects and to enthalpic interactions between the macromolecules and the external interfaces. Studies of the size-dependent physical properties of macromolecules have largely been devoted to linear chain polymers. In this Prospective, we review recent experiments and simulations that describe the structure and fascinating physical properties, from wetting to the glass transition, of star-shaped macromolecules. The properties of these molecules would render them more useful than their linear chain analogs, for some specific applications.

Nanoindentation measurements of the elastic moduli Er of thin polymer films supported by stiff substrates with moduli Es ≫ Er show an increase of Er with decreasing h, for h less than a threshold thickness ht. In the thickness range h < ht , the value of the modulus manifests the influence of various interactions associated with the “stiff” substrate. We show that ht is a function of composition for the miscible blend of polystyrene (PS) and tetramethyl bisphenol-A polycarbonate (TMPC). The modulus Er,TMPC of TMPC films supported by SiOx increases for h < ht(TMPC) ∼ 300 nm while ht(PS) ∼ 450 nm for the modulus Er,PS of PS films, supported by the same substrate. The threshold thicknesses of the blends and the moduli of the blends appear to be reasonably described by an effective medium approximation. This behavior is rationalized in terms of the vibrational force constants f, determined using incoherent neutron scattering experiments, of the materials.

We show that the vitrification of star-shaped polystyrene (PS), of functionality f and molecular weight per arm Mwarm, thin films supported by silicon oxide, SiOx, is strongly dependent on Mwarm and f. When f is small, the vitrification behavior is similar to that of linear-chain PS where the average glass transition, Tg, decreases with decreasing film thickness (ΔTg 0. We show that the overall vitrification behavior of these thin film star-shaped polymers is due to compet...

This work introduces fully π-conjugated gradient copolymers as promising materials to control and stabilize the nanoscale morphology of polymer:fullerene solar cells. Gradient and block sequence copolymers of 3-hexylselenophene (3HS) and 3-hexylthiophene (3HT) are utilized as the donors (D) in bulk-heterojunction (BHJ) solar cells with phenyl-C61-butyric acid methyl ester (PCBM) as the acceptor (A). We show that for the same overall copolymer composition, the ordering of molecular constituents along the copolymer chain (copolymer sequence) significantly influences the nanoscale morphology and phase separation behavior of π-conjugated copolymer:fullerene devices. In addition, energy-filtered transmission electron microscopy (EFTEM) of the blends revealed that relative to the block copolymer:PCBM, the gradient copolymer:PCBM sample formed a more uniform, continuous and interconnected network of polymer fibrils within the acceptor-rich phase, associated with a large D/A interface. Charge extraction of photogenerated carriers by linearly increasing voltage (photo-CELIV) shows that the gradient copolymer:PCBM device possesses the highest initial carrier density, n(0) = (3.92 ± 0.3) × 1018 cm−3, consistent with a larger D/A interfacial area suggested by the observed morphology, albeit at the expense of increased carrier recombination rate. Accelerated degradation studies show that the gradient copolymer:PCBM system maintains the highest efficiency over prolonged heat treatment.

Nanoindentation studies of the mechanical properties of sufficiently thin polymer films, supported by stiff substrates, indicate that the mechanical moduli are generally higher than those of the bulk. This enhancement of the effective modulus, in the thickness range of few hundred nanometers, is indicated to be associated with the propagation and impingement of the indentation tip induced stress field with the rigid underlying substrate; this is the so-called "substrate effect". This behavior has been rationalized completely in terms of the moduli and Poisson's ratios of the individual components, for the systems investigated thus far. Here we show that for thin supported polymer films, in general, information regarding the local chain stiffness and local vibrational constants of the polymers provides an appropriate rationalization of the overall mechanical response of polymers of differing chemical structures and polymer-substrate interactions. Our study should provide impetus for atomistic simulations that carefully account for the role of intermolecular interactions on the mechanical response of supported polymer thin films.

The surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 K above the bulk glass transition temperature ${T}_{g}^{\mathrm{bulk}}$. This behavior, exhibited by star-shaped polystyrenes with functionality $f=8$ arms and molecular weights per arm ${M}_{\mathrm{arm}}l{M}_{e}$ (${M}_{e}$ is the entanglement molecular weight), is shown by molecular dynamics simulations to be associated with a preferential localization of these macromolecules at the free surface. This new phenomenon is in notable contrast to that of linear-chain polymer thin film systems, where the surface relaxations are enhanced in relation to the bulk; this enhancement persists only for a limited temperature range above the bulk ${T}_{g}^{\mathrm{bulk}}$. Evidence of the slow surface dynamics, compared to the bulk, for temperatures well above ${T}_{g}$ and at length and time scales not associated with the glass transition has not previously been reported for polymers.

Although spin casting and chemical surface reactions are the most common methods used for fabricating functional polymer films onto substrates, they are limited with regard to producing films of certain morphological characteristics on different wetting and nonwetting substrates. The matrix-assisted pulsed laser evaporation (MAPLE) technique offers advantages with regard to producing films of different morphologies on different types of substrates. Here, we provide a quantitative characterization, using X-ray diffraction and optical methods, to elucidate the additive growth mechanism of MAPLE-deposited poly(3-hexylthiophene) (P3HT) films on substrates that have undergone different surface treatments, enabling them to possess different wettabilities. We show that MAPLE-deposited films are composed of crystalline phases, wherein the overall P3HT aggregate size and crystallite coherence length increase with deposition time. A complete pole figure constructed from X-ray diffraction measurements reveals that in these MAPLE-deposited films, there exist two distinct crystallite populations: (i) highly oriented crystals that grow from the flat dielectric substrate and (ii) misoriented crystals that preferentially grow on top of the existing polymer layers. The growth of the highly oriented crystals is highly sensitive to the chemistry of the substrate, whereas the effect of substrate chemistry on misoriented crystal growth is weaker. The use of a self-assembled monolayer to treat the substrate greatly enhances the population and crystallite coherence length at the buried interfaces, particularly during the early stage of deposition. The evolution of the in-plane carrier mobilities during the course of deposition is consistent with the development of highly oriented crystals at the buried interface, suggesting that this interface plays a key role toward determining carrier transport in organic thin-film transistors.

The flow of dense suspensions, glasses, and granular materials is heavily influenced by frictional interactions between constituent particles. However, neither hydrodynamics nor friction has successfully explained the full range of flow phenomena in concentrated suspensions. Particles with asperities represent a case in point. Lubrication hydrodynamics fail to completely capture two key rheological properties - namely, that the viscosity increases drastically and the first normal stress difference can switch signs as volume fraction increases. Yet, simulations that account for interparticle friction are also unable to fully predict these properties. Furthermore, experiments show that rheological behavior can vary depending on particle roughness and deformability. We seek to resolve these apparent contradictions by systematically tuning the roughness of model colloids, investigating their viscosity and first normal stress differences under steady shear, and finally generating a rheological state diagram that demonstrates how surface roughness influences the transition between shear thickening and dilatancy. Our simulations, which are in good agreement with the experiments, suggest that friction between rough particles is significant. In addition, we find that roughness progressively lowers the critical conditions required for the onset of shear thickening and dilatancy. Our results thus provides a major contribution in the field of suspension rheology with broad relevance to granular and particulate materials. For instance, particle geometry can be tuned to increase the efficacy of materials that turn solid-like on the application of stimuli. On the other hand, engineers who work with concentrated slurries can now use images of the constituent particles to estimate optimal flow processing conditions.

Interconnectivity of components in three-dimensional networks (3DNs) is essential for stress transfer in hydrogels, aerogels, and composites. Entanglement of nanoscale components in the network relies on weak short-range intermolecular interactions. The intrinsic stiffness and rod-like geometry of nanoscale components limit the cohesive energy of the physical crosslinks in 3DN materials. Nature realizes networked gels differently using components with extensive branching. Branched aramid nanofibers (BANFs) mimicking polymeric components of biological gels were synthesized to produce 3DNs with high efficiency stress transfer. Individual BANFs are flexible, with the number of branches controlled by base strength in the hydrolysis process. The extensive connectivity of the BANFs allows them to form hydro- and aerogel monoliths with an order of magnitude less solid content than rod-like nanocomponents. Branching of nanofibers also leads to improved mechanics of gels and nanocomposites.

We show that due to a substrate-induced orientation of the local morphology of thin supported conjugated polymer films of poly[4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-...

Bulk heterojunction (BHJ) solar cells are fabricated using active material blends of poly(3-hexylthiophene) (P3HT) donor, indene-C60 bisadduct (ICBA) acceptor, and an all-conjugated random copolymer (RCP) additive. By optimizing RCP loading, power conversion efficiencies (PCEs) up to 20% higher than those of a binary P3HT:ICBA mixture are achieved. The improved device characteristics are rationalized in terms of the differences between the photoactive thin film morphologies. Energy-filtered transmission electron micro­scopy reveals that incorporation of the RCP improves the degree of structural order of the BHJ fibrillar network and increases the extent of microphase separation between P3HT and ICBA. Additionally, a combination of atomic force microscopy and X-ray photoelectron spectroscopy analysis indicates segregation of the RCP at the free interface, leading to a shift in the surface potentials measured by Kelvin probe force microscopy. These changes, both in the bulk morphology and in the interfacial composition/energetics, are correlated to improved carrier collection efficiency due to a reduction of non-geminate recombination, which is measured by charge extraction of photo­generated carriers by linearly increasing voltage.

The power conversion efficiency (PCE) of a bulk heterojunction (BHJ) organic solar cell is influenced by the morphology (domain size and connectivity, phase purity, and interfacial structure) of the donor:acceptor blend active layer. The design of experiments to understand interrelationships between structure, transport properties, and device performance remains an important challenge. To this end, we created different types of morphologies in the poly(3-hexylthiophene) (P3HT)/phenyl-C61-butyric acid methyl ester (PC61BM) active layer by exploiting different processing strategies: conventional solvent casting, supercritical carbon dioxide (scCO2) processing, and thermal annealing. We investigated the device characteristics and transport behavior (carrier densities, mobilities and recombination) of samples possessing comparable domain sizes, which exhibited comparable initial carrier densities upon illumination. Notably, however, one morphology exhibited PCE, short circuit current (JSC), and carrier mobili...

The ability to control the wetting properties of a polymeric liquid on a given surface is important for several emerging technological applications including protective coatings, lubricants and sensors. Here we show that star-shaped polystyrene (PS) molecules exhibit notably different wetting properties than their linear analogues of the same chemical structure and their wetting properties can be controlled through changes of their functionality f (number of arms per molecule). Unlike linear chains, the wetting of star-shaped macromolecules is determined by the competition between entropic forces. Wetting is enhanced due to reductions in the loss of entropy upon adsorption of the stars with increasing f; soft colloidal-like entropic repulsion effects suppress the ability of the stars to exhibit a high degree of surface adsorption and to efficiently pack, for sufficiently large values of f. This phenomenon is manifested in the existence of a minimum in the macroscopic contact angle and other related micros...

Diverse processes that include energy conversion, wettability, lubrication, adhesion, and surface-directed phase separation in mixtures fundamentally depend on the structure and dynamics of materials' surfaces and interfaces. We report an unusual phenomenon wherein the surface viscosity of polymer nanocomposites of polystyrene (PS), polyvinyl methyl ether (PVME), and PS-coated gold nanoparticles (PS/PVME/PS-Au) is over an order of magnitude smaller than that of the neat miscible PS/PVME blend. Our X-ray photon correlation spectroscopy studies of the surface dynamics also reveal that the polymer chains manifest dynamics associated with two separate average compositional environments: a PVME-rich region, significantly in excess of its bulk concentration, and a separate PS-rich environment, where the dynamics are approximately 2 orders of magnitude slower. The unusually rapid surface dynamics in the PS/PVME/PS-Au nanocomposite are due largely to the excess PVME chains and the polymer/brush-coated nanoparticle interactions at the free surface.

A study of the poly(vinyl methyl ether) (PVME) segmental dynamics of bulk miscible blends of polystyrene (PS) and PVME reveals that while at high temperatures, T, there is evidence of a single α-relaxation process, at lower T, two separate dominant relaxation processes, associated with the change in structure of the blend with decreasing T, emerge. One relaxation process decreases with a much stronger dependence on T and “freezes” at a temperature comparable to the glass transition temperature, Tg, of the blend measured using differential scanning calorimetry. The other exhibits a weaker T dependence and persists at much lower T, becoming Arrhenius (the so-called α′-process) at sufficiently low T. In thin PVME/PS films confined between aluminum substrates, a new relaxation process, αint, associated with PVME chains that preferentially segregate to the substrates, emerges. These observations are considered in light of the influence of spatial compositional heterogeneities on blend dynamics.

The segmental dynamics of a low glass transition temperature Tg polymer under different conditions of morphological confinement are shown to manifest the influence of the frustration of the local “packing” of chain segments at interfaces of varying curvatures, unique to the morphology. Of particular interest are the polyisoprene (PI) segmental dynamics in polystyrene-b-polyisoprene (PS-b-PI) micelles and in layered onion-like structures in high Tg, “frozen,” polystyrene (PS) hosts. At temperatures close to the Tg of PI domains, the segmental relaxation times of PI chains in the micellar structures, τmicelle, are more than 1 order of magnitude shorter than those of PI chains in the onion-like structures, τonion. These rates are appreciably faster than those of homopolymer PI and of PI in the neat copolymers possessing lamellar and gyroid phases, τhomo ∼ 0.5τlam ∼ 0.5τgyroid, respectively. At high temperatures τhomo ∼ τlam ∼ τgyroid ∼ τonion ∼ τmicelle. These observations are readily reconciled with trends ...

The influence of morphology on the dc conductivity σdc, the charge carrier density n and the out-of-plane mobilities μ were investigated in conjugated polymer films of poly(3-hexylthiophene) (P3HT) using impedance spectroscopy (IS). IS was used for the first time to discern this information from P3HT films. Values of μ, which were found to be film-thickness dependent, increasing with increasing film thickness, h, for films of thickness h > 700 nm, are in excellent agreement with those measured using time-of-flight (ToF) and the method of charge extraction by linearly increasing voltage (CELIV). Both σdc and n are shown to decrease appreciably with increasing h. The thickness dependent trends in μ, σdc and n are consistent with changes in the morphology of these films. Conductive atomic force microscopy (CAFM) provided corroborating information, showing an appreciable dependence of carrier transport on the morphology of P3HT.

Charge-carrier mobilities in poly(3-hexylthiophene) (P3HT) organic thin-film transistors (OTFTs) increase 5-fold when OTFTs composed of P3HT films on trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane (FTS) monolayers supported on SiO2 dielectric substrates (P3HT/FTS/SiO2/Si) are subjected to supercritical carbon dioxide (scCO2) processing. In contrast, carrier mobilities in P3HT/octadecyltrichlorosilane (OTS)/SiO2 OTFTs processed using scCO2 are comparable to mobilities measured in as-cast P3HT/OTS/SiO2/Si devices. Topographical images of the free and buried interfaces of P3HT films reveal that scCO2 selectively alters the P3HT morphology near the buried P3HT/FTS-SiO2 interface; identical processing has negligible effects at the P3HT/OTS-SiO2 interface. A combination of spectroscopic ellipsometry and grazing-incidence X-ray diffraction experiments indicate insignificant change in the orientation distribution of the intermolecular π–π stacking direction of P3HT/FTS with scCO2 processing. The improved mobili...

We propose a sustainable low temperature alternative, using supercritical carbon dioxide (scCO2), to the conventional high temperature thermal annealing protocol for processing poly(3-hexylthiophene) (P3HT)/phenyl-C61-butyric acid methyl ester (PC61BM) organic photovoltaic devices. This new strategy enabled the fabrication of devices that exhibited comparable, and often better, short circuit currents, JSC’s, and efficiencies than those prepared using the conventional heat treatment protocol. While the fill factors (FF) of devices processed using either of the prorocols were comparable, the best performing scCO2 processed devices provided the largest JSC’s. With the use of energy-filtered transmission electron microscopy (EFTEM), and electron energy loss spectroscopy (EELS), we show that the supercritical solvent protocol enabled the formation of similar macro- and nanoscale morphology as the heat treatment protocol. The active materials in the devices with the best efficiencies possessed purer P3HT and PC...

To devise a reliable strategy for achieving specific HOMO and LUMO energy level modulation via alternating donor-acceptor monomer units, we investigate a series of conjugated polymers (CPs) in which the electron withdrawing power of the acceptor group is varied, while maintaining the same donor group and the same conjugated chain conformation. Through experiment and DFT calculations, good correlation is identified between the withdrawing strength of the acceptor group, the HOMO and LUMO levels, and the degree of orbital localization, which allows reliable design principles for CPs. Increasing the acceptor strength results in an enhanced charge transfer upon combination with a donor monomer and a more pronounced decrease of the LUMO level. Moreover, while HOMO states remain delocalized along the polymer chain, LUMO states are strongly localized at specific bonds within the acceptor group. The degree of LUMO localization increases with increasing polymer length, which results in a further drop of the LUMO level and converges to its final value when the number of repeat units reaches the characteristic conjugation length. Based on these insights we designed PBT8PT, which exhibits 6.78% power conversion efficiency after device optimization via the additive assisted annealing, demonstrating the effectiveness of our predictive design approach.

We demonstrate how to tailor the spatial distribution of gold nanoparticles (Au-NPs) of different sizes within polystyrene (PS) thin, supported, film hosts, thereby enabling the connection between the spatial distribution of Au-NPs within the polymer film and the optical properties to be determined. The real, n, and imaginary parts, k, of the complex refractive indices N = n(λ)+ik(λ) of the nanocomposite films were measured as a function of wavelength, λ, using multivariable angle spectroscopic ellipsometry. The surface plasmon response of films containing nearly homogeneous Au-NP distributions were well described by predictions based on classical Mie theory and the Drude model. The optical spectra of samples containing inhomogeneous nanoparticle distributions manifest features associated with differences in the size and interparticle spacings as well as the proximity and organization of nanoparticles at the substrate and free surface.

We study the formation and organization of micelles, of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer chains, in thin film hosts composed of (1) blends of long and short chain polystyrenes, PSL and PSS, of degrees of polymerization PL and PS, respectively (PS < PL), and (2) blends of PSL and a homopolymer with which it is compatible, tetramethyl bisphenol-A polycarbonate (TMPC), of degree of polymerization PTMPC (PTMPC < PL). The role of competing entropic and enthalpic interactions on the block copolymer micelle formation and organization is examined. We show that the average size of the micelle cores, Dcore, decreased with increasing weight fraction of the shorter chain PS component in PS(PS = 125)/PS(PL = 15400) mixtures, for PL≫NPS, NPS is the degree of polymerization of the PS block (the micelle corona). Dcore also decreased with increasing weight fraction of TMPC in TMPC(PTMPC = 122)/PS(PL = 15400) mixtures. The values of Dcore in the TMPC/PSL hosts were smaller than those in PSS...

An important class of functional hard/soft hybrid nanocomposites is formed when nanoparticles (NPs) are induced to self-assemble within the structures of ordered A-b-B diblock copolymers (BCPs). Ba...

The morphologies of thin film blends of polystyrene (PS)-brush coated Au nanoparticles with tetramethyl bisphenol-A polycarbonate (TMPC) were investigated. Our results reveal that entropic effects, associated with the brush/host chain interactions, nanoparticle diameter, D, and asymmetries in monomer sizes of the host and grafted chains, can play a more important role than the favorable PS/TMPC enthalpic interactions toward determining the phase miscibility of the system. A diagram of states is constructed to show the phase separated and dispersed regimes as a function of D, N, the degree of polymerization of the grafted chains, and P, the degree of polymerization of the host chains, at a constant grafting density. These results have important implications on the design of brush coated nanoparticle/homopolymer mixtures for various applications.

The structure of A-b-B diblock copolymer (BCP) thin films is often exploited for “tailoring” the self-assembly of nanoparticles into various geometries, characterized by long-range order. Mechanistically, the nanoparticles are sequestered within the A or B domains of the copolymer, and the domains act as scaffolds to direct the assembly of the nanoparticles. We show that in BCP thin films, which order at suboptimal thicknesses, dislocations play a dominant role in determining the spatial organization of sufficiently large nanoparticles. The nanoparticles preferentially segregate to the core of edge dislocations, which are ubiquitous in these materials. To this end, the two-dimensional planar shape of the islands and holes determine the self-assembled geometry of the nanoparticles. We also show that the so-called “healing length”, λ, increases with film thickness, h, in a manner consistent with λ ∝ h1/2, in accordance with theory. In films of thickness between L < h < 3L, where L is the domain spacing, λ l...

The phase behavior of supported thin film mixtures (h ∼ 120 nm thick) of polystyrene (PS) brush-coated spherical nanoparticle and PS homopolymers is characterized by three regimes, depending on P, the degree of polymerization of the PS host, and N, the degree of polymerization of the grafted chains. Phase separation between the nanoparticles and the host chains occurs in samples for which N N*, preferential segregation of the grafted nanoparticles to the interfaces is accompanied by a structural instability (surface roughening). We identify this as regime I and the former as regime II. The system is miscible in regime III (P N*); the nanoparticles are dispersed throughout the film. There exists a region of partial miscibility that separates regimes I and III. The characteristics of regime I are reminiscent of phase separati...

Chain-grafted Au nanoparticles were synthesized and incorporated into a fluorescent polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), host. We show that control of the Au nanoparticle distribution within MEH-PPV is achieved by manipulating the enthalpic and entropic interactions between the grafted brush layers and the host chains. Further, we show that the fluorescence of these Au/MEH-PPV nanocomposite thin films may be "tailored" by as much as an order of magnitude through changes in the nanoparticle distribution, brush length, and nanoparticle size. The ideas presented herein represent reliable strategies for materials design for devices.