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A new class of donor-acceptor (D-A) copolymers found to produce high charge carrier mobilities competitive with amorphous silicon (>1 cm 2 V -1 s -1 ) exhibit the puzzling microstructure of substantial local order, however lacking long-range order and crystallinity previously deemed necessary for achieving high mobility. Here, we demonstrate the application of low-dose transmission electron microscopy to image and quantify the nanoscale and mesoscale organization of an archetypal D-A copolymer across areas comparable to electronic devices (≈9 μm 2 ). The local structure is spatially resolved by mapping the backbone (001) spacing reflection, revealing nanocrystallites of aligned polymer chains throughout nearly the entire film. Analysis of the nanoscale structure of its ordered domains suggests significant short- and medium-range order and preferential grain boundary orientations. Moreover, we provide insights into the rich, interconnected mesoscale organization of this new family of D-A copolymers by analysis of the local orientational spatial autocorrelations.

We compare the solar cell performance of several polymers with the conventional electron acceptor phenyl-C61-butyric acid methyl ester (PCBM) to fullerenes with one to three indene adducts. We find that the multiadduct fullerenes with lower electron affinity improve the efficiency of the solar cells only when they do not intercalate between the polymer side chains. When they intercalate between the side chains, the multiadduct fullerenes substantially reduce solar cell photocurrent. We use X-ray diffraction to determine how the fullerenes are arranged within crystals of poly-(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) and suggest that poor electron transport in the molecularly mixed domains may account for the reduced solar cell performance of blends with fullerene intercalation., (© 2012 American Chemical Society)

The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells., (© 2011 American Chemical Society)

We describe a series of highly soluble diketo pyrrolo-pyrrole (DPP)-bithiophene copolymers exhibiting field effect hole mobilities up to 0.74 cm(2) V(-1) s(-1), with a common synthetic motif of bulky 2-octyldodecyl side groups on the conjugated backbone. Spectroscopy, diffraction, and microscopy measurements reveal a transition in molecular packing behavior from a preferentially edge-on orientation of the conjugated plane to a preferentially face-on orientation as the attachment density of the side chains increases. Thermal annealing generally reduces both the face-on population and the misoriented edge-on domains. The highest hole mobilities of this series were obtained from edge-on molecular packing and in-plane liquid-crystalline texture, but films with a bimodal orientation distribution and no discernible in-plane texture exhibited surprisingly comparable mobilities. The high hole mobility may therefore arise from the molecular packing feature common to the entire polymer series: backbones that are strictly oriented parallel to the substrate plane and coplanar with other backbones in the same layer.

Grazing incidence X-ray diffraction (GI-XRD) is used to characterize the crystallographic dynamics of low molecular weight (LMW) and high molecular weight (HMW) poly(3-hexylselenophene) (P3HS) films and blend films of P3HS with [6-6-]-phenyl-C(61) -butyric acid methyl ester (PCBM) as a function of 'step-by-step' thermal annealing, from room temperature to 250 °C. The temperature-dependent GIXRD data show how the melting point of P3HS crystallites is decreased by the presence of PCBM. P3HS crystallite domain sizes dramatically increase upon annealing to the P3HS melting temperature. The formation of well-oriented HMW P3HS crystallites with the (100) plane parallel to the substrate (edge-on orientation), when cooled from melt, are observed. We compare the behaviour of P3HS pure and blend films with that of poly(3-hexyl)thiophene (P3HT) pure and PCBM blended films and suggest that the similar temperature dependent behaviour we observe may be a common to polythiophene and related polymers and their blends., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Organic electronics have emerged as a viable competitor to amorphous silicon for the active layer in low-cost electronics. The critical performance of organic electronic materials is closely related to their morphology and molecular packing. Unlike their inorganic counterparts, polymers combine complex repeat unit structure and crystalline disorder. This combination prevents any single technique from being able to uniquely solve the packing arrangement of the molecules. Here, a general methodology for combining multiple, complementary techniques that provide accurate unit cell dimensions and molecular orientation is described. The combination of measurements results in a nearly complete picture of the organic film morphology., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Substantial in-plane crystallinity and dominant face-on stacking are observed in thin films of a high-mobility n-type rylene-thiophene copolymer. Spun films of the polymer, previously thought to have little or no order are found to exhibit an ordered microstructure at both interfaces, and in the bulk. The implications of this type of packing and crystalline morphology are discussed as they relate to thin-film transistors.

Unlike the rounded grains that are well known to form in most soft materials, square grains of microphase-separated lamellae are observed in thin films of a rod-coil block copolymer because of hierarchical structuring originating from the molecular packing of the rods. The square grains are oriented with lamellar layers parallel to the film interface and result from growth along orthogonal low-surface-energy directions as a result of the effects of the tetragonal crystalline lattice that forms within the rod-rich lamellar nanodomains of poly(2,5-di(2'-ethylhexyloxy)-1,4-phenylene vinylene)-b-polyisoprene (PPV-b-PI). These grain shapes form only for a narrow range of coil volume fractions around 72% as a result of kinetic barriers at lower coil fractions and disordering of the lattice at higher coil fractions, and the polydisperse grain size suggests that growth is nucleation-limited. The grains form in both weakly and moderately segregated polymers at all annealing temperatures below the order-disorder transition, and they are observed for all thicknesses at which parallel-oriented grains are grown.

Poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene), PBTTT, is a semiconducting polymer that forms thin film transistors (TFTs) with high field effect mobility on silicon dioxide dielectrics that are treated with alkyltrichlorosilanes ( approximately 0.2 to 0.5 cm2/V s) but forms TFTs with poor mobility on bare silicon dioxide (<0.005 cm2/V s). The microstructure of spin-coated thin films of PBTTT on these surfaces was studied using synchrotron X-ray diffraction and atomic force microscopy. PBTTT crystallizes with lamellae of pi-stacked polymer chains on both surfaces. The crystalline domains are well-oriented relative to the substrate in the as-spun state and become highly oriented and more ordered with thermal annealing in the liquid crystalline mesophase. Although the X-ray scattering from PBTTT is nearly identical on both surfaces, atomic force microscopy showed that the domain size of the crystalline regions depends on the substrate surface. These results suggest that electrical transport in PBTTT films is strongly affected by the domain size of the crystalline regions and the disordered regions between them.

Lithium-salt-doped block copolymers have the potential to serve as solid electrolytes in rechargeable batteries with lithium metal anodes. In this work, we use small-angle X-ray scattering (SAXS) to study the structure of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) doped with bis-(trifluoromethylsulfonyl)amine lithium salt (LiTFSI) during direct current (dc) polarization experiments in lithium-lithium symmetric cells. The block copolymer studied is nearly symmetric in composition, has a total molecular weight of 39 kg mol-1, and exhibits a lamellar morphology at all studied salt concentrations. When ionic current is passed through the electrolyte, a salt concentration gradient forms that induces a spatial gradient in the domain spacing, d. The dependence of d on distance from the positive electrode, x, was determined experimentally by scanning the incident X-ray beam from one lithium electrode to the other. By studying the two-dimensional (2D) SAXS patterns as a function of azimuthal scattering angle, we find that lamellae with PS/PEO interfaces oriented perpendicular to the flow of ionic current (LAM∥) swell and contract to a greater degree than those with interfaces oriented parallel to the current direction (LAM||). While domains with the LAM∥ do not provide direct conducting pathways between the electrodes, our analysis suggests that they play an important role in establishing the salt concentration gradient necessary for sustaining a large ionic current through greater expansion and contraction.

Conjugated block copolymers provide a pathway to achieve thermally stable nanostructured thin films for organic solar cells. We characterized the structural evolution of poly(3-hexylthiophene)-block-poly(diketopyrrolopyrrole-terthiophene) (P3HT-b-DPPT-T) from solution to nanostructured thin films. Aggregation of the DPPT-T block of P3HT-b-DPPT-T was found in solution by small-angle X-ray scattering with the P3HT block remaining well-solvated. The nanostructure in thin films was determined using a combination of wide and small-angle X-ray scattering techniques as a function of processing conditions. The structure in solution controlled the initial nanostructure in spin-cast thin films, allowing subsequent thermal annealing processes to further improve the ordering. In contrast to the results for thin films, nanostructural ordering was not observed in the bulk samples by small-angle X-ray scattering. These results suggest the importance of controlling solvent induced aggregation in forming nanostructured thin films of conjugated block copolymers.

All-polymer solar cells (all-PSCs) offer improved morphological and mechanical stability compared with those containing small-molecule-acceptors (SMAs). They can be processed with a broader range of conditions, making them desirable for printing techniques. In this study, we report a high-performance polymer acceptor design based on bithiazole linker (PY-BTz) that are on par with SMAs. We demonstrate that bithiazole induces a more coplanar and ordered conformation compared to bithiophene due to the synergistic effect of non-covalent backbone planarization and reduced steric encumbrances. As a result, PY-BTz shows a significantly higher efficiency of 16.4% in comparison to the polymer acceptors based on commonly used thiophene-based linkers (i.e., PY-2T, 9.8%). Detailed analyses reveal that this improvement is associated with enhanced conjugation along the backbone and closer interchain π-stacking, resulting in higher charge mobilities, suppressed charge recombination, and reduced energetic disorder. Remarkably, an efficiency of 14.7% is realized for all-PSCs that are solution-sheared in ambient conditions, which is among the highest for devices prepared under conditions relevant to scalable printing techniques. This work uncovers a strategy for promoting backbone conjugation and planarization in emerging polymer acceptors that can lead to superior all-PSCs. All-polymer solar cells comprising both polymeric donors and acceptors offer better morphological and mechanical stability, and a broader processing window for printing. Here, the authors report a polymer acceptor based on bithiazole linker with more coplanar and ordered molecular conformation. [ABSTRACT FROM AUTHOR]

Stretchable polymer semiconductors (PSCs) have seen great advancements alongside the development of soft electronics. But it remains a challenge to simultaneously achieve high charge carrier mobility and stretchability. Herein, we report the finding that stretchable PSC thin films (<100-nm-thick) with high stretchability tend to exhibit multi-modal energy dissipation mechanisms and have a large relative stretchability (rS) defined by the ratio of the entropic energy dissipation to the enthalpic energy dissipation under strain. They effectively recovered the original molecular ordering, as well as electrical performance, after strain was released. The highest rS value with a model polymer (P4) exhibited an average charge carrier mobility of 0.2 cm2V−1s−1 under 100% biaxial strain, while PSCs with low rS values showed irreversible morphology changes and rapid degradation of electrical performance under strain. These results suggest rS can be used as a parameter to compare the reliability and reversibility of stretchable PSC thin films. Stretchable polymer semiconductors with high mechanical and electrical properties are challenging to develop. Wu et al. show that reversible molecular ordering under strain important for performance optimization and relative stretchability can be used to compare the relative strain tolerance of materials. [ABSTRACT FROM AUTHOR]

The mass density profile from thin (∼25 Å) layers of polymer molecules adsorbed on amorphous carbon thin films is determined from measurements of the specular reflectivity of x rays. Important information on the conformation of the polymer molecules is obtained from the density profile (average density as a function of position above the surface). The polymer is a perfluoropolyether (PFPE) with piperonyl end groups and has a molecular weight of 2000–3000 Daltons. Three samples are measured: a nonbonded sample with an approximately 25 Å layer applied by dipping, a bonded sample with the layer applied by dipping but followed by a process to attach the molecule to the carbon, and a cleaned sample which is the nonbonded sample after the polymer had been removed. The density profile of the nonbonded polymer shows that the density within 10 Å of the carbon surface is ∼1.6 gm/cc, which is smaller than the density in the region between 10 and 25 Å (∼1.8 gm/cc). This indicates that the less dense piperonyl end groups are preferentially adsorbed near the carbon surface, which provides a possible explanation of the observation that the addition of the piperonyl end group to PFPE improves adhesion of the polymer to surfaces. The bulk-like density in the region between 10 and 25 Å and the compactness of the layer suggest that the preponderance of molecules have both end groups preferentially adsorbed; consequently, the PFPE chains remain close to the surface. The data from the bonded and nonbonded polymer layers are essentially the same, which indicates the molecular conformation is not strongly affected by the bonding treatment. [ABSTRACT FROM AUTHOR]

Abstract: The introduction of oligomeric polystyrene (PS) side chains into the conjugated backbone is proven to enhance the processability and electronic properties of semiconducting polymers. Here, two series of donor and acceptor polymers are prepared with different molar percentages of PS side chains to elucidate the effect of their substitution arrangement on the all‐polymer solar cell performance. The observed device performance is lower when the PS side chains are substituted on the donor polymer and higher when on the acceptor polymer, indicating a clear arrangement effect of the PS side chain. The incorporation of PS side chains to the acceptor polymer contributes to the decrease in phase separation domain size in the blend films. However, the reduced domain size was still an order of magnitude larger than the typical exciton diffusion length. A detailed morphological study together with the estimation of solubility parameter of the pristine PS, donor, and acceptor polymers reveals that the relative value of solubility parameter of each component dominantly contributes to the purity of the phase separated domain, which strongly impacts the amount of generated photocurrent and overall solar cell performance. This study provides an understanding of the design strategies to improve the all‐polymer solar cells. [ABSTRACT FROM AUTHOR]

The solid-state packing and polymer orientation relative to the substrate are key properties to control in order to achieve high charge carrier mobilities in organic field effect transistors (OFET). Intuitively, shorter side chains are expected to yield higher charge carrier mobilities because of a denser solid state packing motif and a higher ratio of charge transport moieties. However our findings suggest that the polymer chain orientation plays a crucial role in high-performing diketopyrrolopyrrole-based polymers. By synthesizing a series of DPP-based polymers with different branched alkyl side chain lengths, it is shown that the polymer orientation depends on the branched alkyl chain lengths and that the highest carrier mobilities are obtained only if the polymer adopts a mixed face-on/edge-on orientation, which allows the formation of 3D carrier channels in an otherwise edge-on-oriented polymer chain network. Time-of-flight measurements performed on the various polymer films support this hypothesis by showing higher out-of-plane carrier mobilities for the partially face-on-oriented polymers. Additionally, a favorable morphology is mimicked by blending a face-on polymer into an exclusively edge-on oriented polymer, resulting in higher charge carrier mobilities and opening up a new avenue for the fabrication of high performing OFET devices. [ABSTRACT FROM AUTHOR]

Investigations on the impact of interfacial modification on organic optoelectronic device performance often attribute the improved device performance to the optoelectronic properties of the modifier. A critical assumption of such conclusions is that the organic active layer deposited on top of the modified surface (interface) remains unaltered. Here the validity of this assumption is investigated by examining the impact of substrate surface properties on the morphology of poly(3-hexylthiophene):1-(3-methoxycarbonyl)-propyl-1-phenyl-[6,6]C61 (P3HT:PCBM) bulk-heterojunction (BHJ). A set of four nickel oxide and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTL) with contrasting surface properties and performance in organic photovoltaic (OPV) devices is studied. Differences in vertical composition variation and structural morphologies are observed across the samples, but only in the near-interface region of <∼20 nm. Near-interface differences in morphology are most closely correlated with surface polarity and surface roughness of the HTL. Surface polarity is more influenced by surface composition than surface roughness and crystal structure. These findings corroborate the previously mentioned conclusions that the differences in device performance observed in solar cells employing these HTLs are dominated by the electronic properties of the HTL/organic photoactive active layer interface and not by unintentional alteration in the BHJ active layer morphology. [ABSTRACT FROM AUTHOR]

The bulk heterojunction (BHJ) solar cell performance of many polymers depends on the polymer molecular weight ( Mn) and the solvent additive(s) used for solution processing. However, the mechanism that causes these dependencies is not well understood. This work determines how Mn and solvent additives affect the performance of BHJ solar cells made with the polymer poly(di(2-ethylhexyloxy)benzo[1,2- b:4,5- b′]dithiophene- co-octylthieno[3,4- c]pyrrole-4,6-dione) (PBDTTPD). Low Mn PBDTTPD devices have exceedingly large fullerene-rich domains, which cause extensive charge-carrier recombination. Increasing the Mn of PBDTTPD decreases the size of these domains and significantly improves device performance. PBDTTPD aggregation in solution affects the size of the fullerene-rich domains and this effect is linked to the dependency of PBDTTPD solubility on Mn. Due to its poor solubility high Mn PBDTTPD quickly forms a fibrillar polymer network during spin-casting and this network acts as a template that prevents large-scale phase separation. Furthermore, processing low Mn PBDTTPD devices with a solvent additive improves device performance by inducing polymer aggregation in solution and preventing large fullerene-rich domains from forming. These findings highlight that polymer aggregation in solution plays a significant role in determining the morphology and performance of BHJ solar cells. [ABSTRACT FROM AUTHOR]

Thin films of polymer semiconductors are being intensively investigated for large-area electronics applications such as light-emitting diodes, photovoltaic cells and thin-film transistors. Understanding the relationship between film morphology and charge transport is key to improving the performance of thin-film transistors. Here we use X-ray diffraction rocking curves to provide direct evidence for highly oriented crystals at the critical buried interface between the polymer and the dielectric where the current flows in thin-film transistors. Treating the substrate surface with self-assembled monolayers significantly varies the concentration of these crystals. We show that the polymer morphology at the buried interface can be different from that in the bulk of the thin films, and provide insight into the processes that limit charge transport in polythiophene films. These results are used to build a more complete model of the relationship between chain packing in polymer thin-films and charge transport. [ABSTRACT FROM AUTHOR]

Grazing-incidence X-ray diffraction and rocking scans have quantified the structure of poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester in the active layers of organic solar cells. Our study reveals that the device JSCcorrelates with the local structural development of pure PCBM and, to second order, the extent of out-of-plane P3HT π-stacking. [ABSTRACT FROM AUTHOR]

The effects of the roughness of the gate dielectric on the performance of thin film transistors (TFTs) fabricated with poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b] thiophene) (PBTTT-C16) were examined. The field effect mobility of coplanar TFTs made with PBTTT-C16 and plasma-enhanced chemical vapor deposited SiO2/SiNx dielectrics decreased nearly exponentially with surface roughness. Films of PBTTT-C16 have similar crystalline structure on smooth and rough surfaces, but the domain size decreases with increasing roughness. Surface roughness was found to have less of an impact on field effect mobility than the chemical treatment of the dielectric. [ABSTRACT FROM AUTHOR]

The authors report a significant dependence of the morphology and charge carrier mobility of poly(2,5-bis(3-dodecylthiophene-2-yl)thieno[3,2-b]thiophene) (pBTTT) films on the substrate surface chemistry upon heating into its liquid crystal phase. In contrast with films on bare silicon oxide surfaces, pBTTT films on oxide functionalized with octyltrichlorosilane exhibit substantial increases in the lateral dimensions of molecular terraces from nanometers to micrometers, increased orientational order, and higher charge carrier mobility. The large-scale crystallinity of this polymer plays an important role in the high carrier mobility observed in devices, but renders it more sensitive to substrate surface chemistry than other conjugated polymers. [ABSTRACT FROM AUTHOR]

Presents the results of the study on near-surface alignment of polymer molecules caused by the rubbing of a polyimide film. Use of grazing-incidence X-ray scattering (GIXS); Derivation of the polyimide used in the experiment; Observation of X-ray scattering.

To better understand the correlation of the dielectric properties with the photovoltaic response in conjugated polymer:fullerene bulk heterojunction materials, the concept of introducing minimal structural change is employed to increase the polymer dielectric constant via polar cyano groups added to the end of butyl or octyl side chains in the poly(dithienosilole‐thienopyrrolodione) system. Density functional theory calculations confirm that the polar groups do not affect the polymer electronic structure but can lead to an increase in overall dipole moment depending on the polymer chain conformation. Despite the increased dielectric constant (from 2.7 to 4.3 for cyano‐octyl side chains and from 2.7 to 3.2 for the cyano‐butyl analogues), the device characteristics employing the cyano‐containing polymers are inferior to those of the devices made with unfunctionalized alkyl chains. It is found that the hole mobilities for the cyano‐containing polymers are two orders of magnitude lower compared to those for the parent polymers and suggest this is due to an increase in energetic disorder caused by the strong local permanent dipoles associated with the cyano groups. The study highlights the complexity in the relationship between the dielectric constant of organic materials, the morphologies that are induced, and their photovoltaic performance. Introducing polar cyano groups to the end of dithienosilole‐thienopyrrolodione polymer side chains leads to an increase in polymer dielectric constant, without significantly affecting the optical gaps and energy levels. However, this structural modification results in inferior device parameters and ultimately lower power conversion efficiencies, because of the drastic decrease in hole mobilities which is caused by higher energetic disorders. [ABSTRACT FROM AUTHOR]

X-ray reflectivity has been used to measure the roughness of perfluoropolyether (PFPE) polymer films on silicon substrates and carbon overcoats. For PFPE on smooth silicon, we find that the rms roughness of the PFPE-air interface increases slowly from about 2 to 4 Å as PFPE thickness increases from 5 to 33 Å. This increase is consistent with capillary waves roughening the polymer film, but inconsistent with current theories for the dewetting of polymer films. For PFPE on the rougher surface of amorphous hydrogenated carbon, we find that the PFPE polymer smoothes the surface with the rms roughness decreasing from 9 to 4 Å. We also discuss the implications of these results on the limits of disk drive technology. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Identifying how small molecular acceptorspack with polymer donorsin thin and thick (bulk) films is critical to understanding the natureof electrical doping by charge transfer. In this study, the packingstructure of the molecular acceptor tetrafluorotetracyanoquinodimethane(F4TCNQ) with the semiconducting polymer poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-C14) is examined. A combinationof solid-state NMR, synchrotron X-ray scattering, and optical spectroscopywas used to determine the packing motif for blends of PBTTT-C14and F4TCNQ in thin and bulk films. These resultsindicate that F4TCNQ and PBTTT-C14order ina cofacial arrangement where charge transfer is near 100% efficientin the solid state. These results provide crucial insights into thestructures and compositions of ordered domains in doped semiconductingpolymers and suggest a model for the microstructure where the locationof the molecular acceptors are correlated rather than randomly dispersed. [ABSTRACT FROM AUTHOR]

Efficient charge carrier transport in organic field-effect transistors (OFETs) often requires thin films that display long-range order and close π–π packing that is oriented in-plane with the substrate. Although some polymers have achieved high field-effect mobility with such solid-state properties, there are currently few general strategies for controlling the orientation of π-stacking within polymer films. In order to probe structural effects on polymer-packing alignment, furan-containing diketopyrrolopyrrole (DPP) polymers with similar optoelectronic properties were synthesized with either linear hexadecyl or branched 2-butyloctyl side chains. Differences in polymer solubility were observed and attributed to variation in side-chain shape and polymer backbone curvature. Averaged field-effect hole mobilities of the polymers range from 0.19 to 1.82 cm2/V·s, where PDPP3F-C16 is the least soluble polymer and provides the highest maximum mobility of 2.25 cm2/V·s. Analysis of the films by AFM and GIXD reveal that less soluble polymers with linear side chains exhibit larger crystalline domains, pack considerably more closely, and align with a greater preference for in-plane π–π packing. Characterization of the polymer solutions prior to spin-coating shows a correlation between early onset nanoscale aggregation and the formation of films with highly oriented in-plane π-stacking. This effect is further observed when nonsolvent is added to PDPP3F-BO solutions to induce aggregation, which results in films with increased nanostructural order, in-plane π–π orientation, and field-effect hole mobilities. Since nearly all π-conjugated materials may be coaxed to aggregate, this strategy for enhancing solid-state properties and OFET performance has applicability to a wide variety of organic electronic materials. [ABSTRACT FROM AUTHOR]

We quantify the degree of paracrystalline disorder in the π-π stacking direction of crystallites of a high performing semicrystalline semiconducting polymer with advanced x-ray line-shape analysis. Using density functional theory calculations to provide input to a simple tight-binding model, we obtain the density of states of a system of π-π stacked polymer chains with increasing amounts of paracrystalline disorder. We find that, for an aligned film of PBTTT, the paracrystalline disorder is 7.3%. This type of disorder induces a tail of trap states with a breadth of ∼100 meV as determined through calculation. This finding agrees with previous device modeling and provides physical justification for the mobility edge model. [ABSTRACT FROM AUTHOR]

The blend films of small-molecule semiconductors with insulating polymers exhibit not only excellent solution processability but also superior performance characteristics in organic thin-film transistors (OTFTs) over those of neat small-molecule semiconductors. To understand the underlying mechanism, we studied triethylsilylethynyl anthradithiophene (TESADT) with small amounts of impurity formed by weak UV exposure. OTFTs with neat impure TESADT had drastically reduced field-effect mobility (<10-5 cm²/(V s)), and a disappearance of the high-temperature crystal phase was observed for neat impure TESADT. However, the mobility of the blend films of the UV-exposed TESADT with poly(a-methylstyrene) (PαMS) is recovered to that of a fresh TESADT-PαMS blend (0.040 cm²/(V s)), and the phase transition characteristics partly return to those of fresh TESADT films. These results are corroborated by OTFT results on "aged" TIPS-pentacene. These observations, coupled with the results of neutron reflectivity study, indicate that the formation of a vertically phase-separated layer of crystalline small-molecule semiconductors allows the impurity species to remain preferentially in the adjacent polymer- rich layer. Such a "zone-refinement effect" in blend semiconductors effectively removes the impurity species that are detrimental to organic electronic devices from the critical charge-transporting interface region. [ABSTRACT FROM AUTHOR]

A comparison of three samples of poly(3-hexylthiophene) having regioregularities of 86, 90, and 96% is used to elucidate the effect of regioregularity on polymer-fullerene-composite solar cell performance. It is observed that polymer samples with lower regioregularity are capable of generating fullerene composites that exhibit superior thermal stability. The enhanced thermal stability of the composites is attributed to a lower driving force for polymer crystallization in the less regioregular polymer samples, which is supported with two-dimensional grazing incidence X-ray scattering and differential scanning calorimetry measurements. Furthermore, it is demonstrated that all three polymer samples are capable of generating solar cells with equivalent peak efficiencies of ∼4% in blends with [6,6]-phenyl-C61-butyric acid methyl ester. While it may be non-intuitive that polymers with lower regioregularity can exhibit higher efficiencies, it is observed that the charge-carrier mobility of the three polymers is on the same order of magnitude (10-4 cm2 V-1 s-1) when measured from the space-charge-limited current, suggesting that highly regioregular and crystalline polythiophenes are not required in order to effectively transport charges in polymer solar cells. Overall, these results suggest a design principle for semicrystalline conjugated polymers in fullerene-composite solar cells in which crystallization-driven phase separation can be dramatically suppressed via the introduction of a controlled amount of disorder into the polymer backbone. [ABSTRACT FROM AUTHOR]