Reduced Bimolecular Recombination in Blade-Coated, High-Efficiency, Small-Molecule Solar Cells.

To realize the full promise of solution deposited photovoltaic devices requires processes compatible with high-speed manufacturing. We report the performance and morphology of blade-coated bulk heterojunction devices based on the small molecule donor p-DTS(FBTTh2)2 when treated with a post-deposition solvent vapor annealing (SVA) process. SVA with tetrahydrofuran improves the device performance of blade-coated films more than solvent additive processing (SA) with 1,8-diiodooctane. In spin-coating, SA and SVA achieve similar device performance. Our optimized, blade coated, SVA devices achieve power conversion efficiencies over 8 % and maintain high efficiencies in films up to ≈ 250 nm thickness, providing valuable resilience to small process variations in high-speed manufacturing. Using impedance spectroscopy, we show that this advantageous behavior originates from highly suppressed bimolecular recombination in the SVA-treated films. Electron microscopy and grazing-incidence X-ray scattering experiments show that SA and SVA both produce highly crystalline donor domains, but SVA films have a radically smaller domain size compared to SA films. We attribute the different behavior to variations in initial nucleation density and relative ability of SVA and SA to control subsequent crystal growth.

Film morphology evolution during solvent vapor annealing of highly efficient small molecule donor/acceptor blends.

Solution-processable small molecule photovoltaics based on the novel molecular donor, benzodithiophene terthiophene rhodanine (BTR), recently have shown maximum power conversion efficiencies above 8 % for active layer thicknesses up to 400 nm, using post process solvent vapor annealing (SVA) with tetrahydrofuran (THF). Here we report an in-situ study on the morphology evolution during SVA using the moderate solvent THF and the good solvent chloroform (CF). The combination of real-time grazing incidence X-ray diffraction (GIXD) and grazing incidence small angle X-ray scattering (GISAXS) allows us to draw a complete picture of the evolution of crystallinity and phase purity during post process annealing. We find that the relative crystallinity compared to the as-cast films is only modestly affected by SVA and solvent choice. However, both the phase purity and the characteristic domain sizes within the film vary significantly and are controlled by the solvent quality as well as exposure time. Using THF, films with high phase purity and desirable characteristic length scales of about 30 nm can be achieved, while the use of CF rapidly leads to excessive film coarsening and less preferable domain sizes on the order of 60 nm, too large for optimized charge separation.

Morphology Changes Upon Scaling a High-Efficiency, Solution-Processed Solar Cell From Spin-Coating to Roll-to-Roll Coating.

Solution processing via roll-to-roll (R2R) coating promises a low cost, low thermal budget, sustainable revolution for the production of solar cells. Poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-di(2-octyldodecyl)-2,2';5',2″;5″,2‴-quaterthiophen-5,5-diyl)], PffBT4T-2OD, has recently been shown to achieve high power conversion efficiency (>10%) paired with multiple acceptors when thick films are spun-coat from hot solutions. We present detailed morphology studies of PffBT4T-2OD based bulk heterojunction films deposited by the volume manufacturing compatible techniques of blade-coating and slot-die coating. Significant aspects of the film morphology, the average crystal domain orientation and the distribution of the characteristic phase separation length scales, are remarkably different when deposited by the scalable techniques vs spun-coat. Yet, we find that optimized blade-coated devices achieve PCE >9.5%, nearly the same as spun-coat. These results challenge some widely accepted propositions regarding what is an optimal BHJ morphology and suggest the hypothesis that diversity in the morphology that supports high performance may be a characteristic of manufacturable systems, those that maintain performance when coated thicker than ≈200 nm. In situ measurements reveal the key differences in the solidification routes for spin- and blade- coating leading to the distinct film structures.

Visualization of phase evolution in model organic photovoltaic structures via energy-filtered transmission electron microscopy.

The morphology of the active layer in an organic photovoltaic bulk-heterojunction device is controlled by the extent and nature of phase separation during processing. We have studied the effects of fullerene crystallinity during heat treatment in model structures consisting of a layer of poly(3-hexylthiophene) (P3HT) sandwiched between two layers of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Utilizing a combination of focused ion-beam milling and energy-filtered transmission electron microscopy, we monitored the local changes in phase distribution as a function of annealing time at 140 °C. In both cases, dissolution of PCBM within the surrounding P3HT was directly visualized and quantitatively described. In the absence of crystalline PCBM, the overall phase distribution remained stable after intermediate annealing times up to 60 s, whereas microscale PCBM aggregates were observed after annealing for 300 s. Aggregate growth proceeded vertically from the substrate interface via uptake of PCBM from the surrounding region, resulting in a large PCBM-depleted region in their vicinity. When precrystallized PCBM was present, amorphous PCBM was observed to segregate from the intermediate P3HT layer and ripen the crystalline PCBM underneath, owing to the far lower solubility of crystalline PCBM within P3HT. This process occurred rapidly, with segregation already evident after annealing for 10 s and with uptake of nearly all of the amorphous PCBM by the crystalline layer after 60 s. No microscale aggregates were observed in the precrystallized system, even after annealing for 300 s.

Anisotropic, hierarchical surface patterns via surface wrinkling of nanopatterned polymer films.

By combining surface wrinkling and nanopatterned polymer films, we create anisotropic, hierarchical surfaces whose larger length-scale (wrinkling wavelength) depends intimately on the geometry and orientation of the smaller length-scale (nanopattern). We systematically vary the pattern pitch, pattern height, and residual layer thickness to ascertain the dependence of the wrinkling wavelength on the nanopattern geometry. We apply a composite mechanics model to gain a quantitative understanding of the relationship between the geometric parameters and the anisotropy in wrinkling wavelength. Additionally, these results shed light on the effect of surface roughness, as represented by the nanopattern, on the metrology of thin films via surface wrinkling.

Molecular order in high-efficiency polymer/fullerene bulk heterojunction solar cells.

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.

Thermally reversible surface morphology transition in thin diblock copolymer films.

Many phase transitions exhibit ordering transitions at the boundary of the material that are distinct from its interior where intermolecular interactions can be significantly different. The present work considers the existence of a surface thermodynamic order-order transition between two distinct morphologies in thin block copolymer (BCP) films that are of interest in nanomanufacturing applications. Specifically, we find a thermally reversible interfacial transition between sphere-like structures and cylinders in flow-coated films of poly(styrene-block-methyl methacrylate) (PS-b-PMMA), where the BCP forms a cylinder microphase in the bulk. We present direct evidence from atomic force microscopy (AFM) of ion-etched films and grazing-incidence small-angle X-ray scattering (GISAXS) on films without etching, which shows that the order-order transition is restricted to the outer layer of the film, while the film interior remains in the cylinder state. Moreover, we find this order-order transition to be insensitive to film thickness over the range investigated (40-170 nm). This morphological transition is of importance in characterizing the thermodynamics and dynamics of thin BCP films used as templates in nanomanufacturing applications.

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

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

Relaxation behavior of polymer structures fabricated by nanoimprint lithography.

We study the decay of imprinted polystyrene (PS) patterns under thermal annealing using light diffraction. The first-order diffraction intensity from the imprinted gratings was measured as a function of annealing time. A local intensity maximum is observed as a function of annealing time. This "abnormal" intensity variation can be qualitatively understood, using rigorous coupled wave approximation calculations, as a characteristic diffraction from patterns with specific shape/height. We demonstrate that this diffraction anomaly can be used to characterize the temperature dependence of the pattern decay rate. The activation energies of the pattern decay are found to be similar to those of the segmental and chain relaxations. Comparisons between PS samples of different molecular mass reveal that the patterns decay through different mechanisms. For unentangled PS, the decay of the imprinted pattern follows the surface-tension-driven viscous flow, with a viscosity similar to the steady-state viscosity. However, for highly entangled PS, large residual stresses introduced from the imprinting process cause the pattern to decay much faster than expected from surface-tension-driven viscous flow.