We report quantitative measurements of ordering, molecular orientation, and nanoscale morphology in the active layer of bulk heterojunction (BHJ) organic photovoltaic cells based on a thieno[3,4-b]thiophene-alt-benzodithiophene copolymer (PTB7), which has been shown to yield very high power conversion efficiency when blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC(71)BM). A surprisingly low degree of order was found in the polymer-far lower in the bulk heterojunction than in pure PTB7. X-ray diffraction data yielded a nearly full orientation distribution for the polymer π-stacking direction within well-ordered regions, revealing a moderate preference for π-stacking in the vertical direction ("face-on"). By combining molecular orientation information from polarizing absorption spectroscopies with the orientation distribution of ordered material from diffraction, we propose a model describing the PTB7 molecular orientation distribution (ordered and disordered), with the fraction of ordered polymer as a model parameter. This model shows that only a small fraction (≈20%) of the polymer in the PTB7/PC(71)BM blend is ordered. Energy-filtered transmission electron microscopy shows that the morphology of PTB7/PC(71)BM is composed of nanoscale fullerene-rich aggregates separated by polymer-rich regions. The addition of diiodooctane (DIO) to the casting solvent, as a processing additive, results in smaller domains and a more finely interpenetrating BHJ morphology, relative to blend films cast without DIO.

The development of flexible and physically robust organic solar cells requires detailed knowledge of the mechanical behavior of the heterogeneous material stack. However, in these devices there has been limited research on the mechanical properties of the active organic layer. Here, two critical mechanical properties, stiffness and ductility, of a widely studied organic solar cell active layer, a blend film composed of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) are reported. Processing conditions are varied to produce films with differing morphology and correlations are developed between the film morphology, mechanical properties and photovoltaic device performance. The morphology is characterized by fitting the absorption of the P3HT:PCBM films to a weakly interacting H‐aggregate model. The elastic modulus is determined using a buckling metrology approach and the crack onset strain is determined by observing the film under tensile strain using optical microscopy. Both the elastic modulus and crack onset strain are found to vary significantly with processing conditions. Processing methods that result in improved device performance are shown to decrease both the compliance and ductility of the film.

Optimized spin-coating and blade-coating are found to produce similar performance yet notably different morphologies.

A consensus is emerging that mixed phases are present in bulk heterojunction organic photovoltaic (OPV) devices. Significant insights into the mixed phases have come from bilayer stability measurements, in which an initial sample consisting of material pure layers of donor and acceptor is thermally treated, resulting in swelling of one layer by the other. We present a comparative study of the stability of polymer/fullerene bilayers using two common OPV polymer donors poly(3-hexylthiophene), P3HT, and poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)], PCDTBT, and four fullerene acceptors phenyl-C61-butyric acid methyl ester, phenyl-C71-butyric acid methyl ester, [60]PCBM bis-adduct, and indene C60 bis-adduct. Using in situ spectroscopic ellipsometry to characterize the quasi-steady state behavior of the films, we find that the polymer glass transition temperature (T g) is critical to the bilayer stability, with no significant changes occurring below T g of the high T g PCDTBT. Above the polymer T g, we find the behavior is irreversible and most consistent with swelling of the polymer by the fullerene, constrained by tie chains in the polymer network and influenced by the rubbery dynamics of the mixed region. The swelling varies significantly with the nature of the fullerene and the polymer. Across the eight systems studied, there is no clear relationship between swelling and OPV device performance. The relationship between the observed swelling and the underlying fullerene–polymer miscibility is explored via Flory–Rehner theory.

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.

The mixing behavior of the hole- and electron-transporting materials in bulk heterojunction (BHJ) organic photovoltaic (OPV) blends plays a key role in determining the nanoscale morphology, which is believed to be a decisive factor in determining device performance. We present a systematic investigation of the mixing behavior between poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in model multilayer structures. The bilayer structures are composed of amorphous PCBM that is mechanically laminated to different P3HT layers with varying degrees of crystallinity. We find that mixing is significantly decreased as the crystallinity of P3HT is increased. The mixing behavior can be explained as resulting from (1) nearly complete miscibility of PCBM with amorphous P3HT (based on our results from regiorandom P3HT) and (2) the existence of tie chains between crystalline P3HT domains that restrain the swelling of the P3HT layer by PCBM. We also introduce a unique PCBM–P3HT–PCBM trilayer structure where one of the PCBM layers is highly crystalline. The crystalline PCBM dramatically alters the mixing behavior. Initial mixing of the amorphous PCBM into P3HT is followed by rapid cold crystallization at the crystalline PCBM layer, which depletes the PCBM in the P3HT layer. These bilayer and trilayer experiments illustrate that mixing of P3HT and PCBM is influenced by multiple factors, such as the semicrystalline nature of P3HT (overall crystallinity, characteristics of amorphous chains) and phase (amorphous or crystalline) of the PCBM.

Results are presented from theoretical and experimental infrared (IR) spectroscopy studies of the microstructures of poly(silsesquioxane)s (PSSQs) of varying chemical composition. The calculated IR spectra show two distinct asymmetric Si-O-Si stretch vibration bands for models of complete polyhedral cages, incomplete open cages, and short ladder structures. Close analyses of the calculated results indicate that the higher frequency IR band at about 1150 cm -1 is derived from the parallel asymmetric Si-O-Si stretch vibration mode in the (Si-O) n ring subunit while the lower frequency band at about 1050 cm -1 is due to the asymmetric Si-O-Si stretch symmetric with respect to the inversion point at the center of the (Si-O) n ring and is absent in highly symmetric cage structures. Experimentally, poly(methylsilsesquioxane) (PMSQ), poly(isobutylsilsesquioxane) (PiBSQ), and poly(phenylsilsesquioxane) (PPhSQ) exhibit a varying tendency of cage-like structures, rather than ladder structures, in as-polymerized samples. When the thermal conversion (curing) temperature is increased to 400 °C, the microstructure of PMSQ in thin solid films transforms from open cage-like structure toward a random network with lower symmetry. This change in microstructure is caused by the secondary condensation reaction and the evaporation of cage structures, and the effect of cage evaporation becomes most pronounced for PiBSQ films, which are mostly comprised of cage-like structures that evaporate around 280 °C. In comparison, PPhSQ films retain cage-like structure upon curing to 400 °C as a result of the high evaporation temperature (ca. 500 °C) of the cages.

Recent demonstration of mobilities in excess of 10 cm2 V–1 s–1 have energized research in solution deposition of polymers for thin film transistor applications. Due to the lamella motif of most soluble, semiconducting polymers, the local mobility is intrinsically anisotropic. Therefore, fabrication of aligned films is of interest for optimization of device performance. Many techniques have been developed to control film alignment, including solution deposition via directed flows and deposition on topologically structured substrates. We report device and detailed structural analysis (ultraviolet–visible absorption, IR absorption, near-edge X-ray absorption (NEXAFS), grazing incidence X-ray diffraction, and atomic force microscopy) results from blade coating two high performing semiconducting polymers on unpatterned and nanostructured substrates. Blade coating exhibits two distinct operational regimes: the Landau–Levich or horizontal dip coating regime and the evaporative regime. We find that in the evaporative deposition regime, aligned films are produced on unpatterned substrates with the polymer chain director perpendicular to the coating direction. Both NEXAFS and device measurements indicate the coating induced orientation is nucleated at the air interface. Nanostructured substrates produce anisotropic bottom contact devices with the polymer chain at the buried interface oriented along the direction of the substrate grooves, independent of coating regime and coating direction. Real time studies of film drying establish that alignment occurs at extremely high polymer volume-fraction conditions, suggesting mediation via a lyotropic phase. In all cases the final films appear to exhibit high degrees of crystalline order. The independent control of alignment at the air and substrate interfaces via coating conditions and substrate treatment, respectively, enable detailed assessment of structure–function relationships that suggest the improved performance of the nanostructure aligned films arise from alignment of the less ordered material in the crystallite interphase regions.