Despite having surpassed 10% power conversion efficiency (PCE), widely held as the threshold for commercial viability, high performance organic photovoltaics (OPVs) are still mostly constrained to lab-scale devices fabricated by spin coating. Efforts to produce scalable printed OPVs trail significantly in efficiency, highlighting the need to better understand the processing-morphology-performance relationship in the context of linear printing processes. Here we investigate the OPV system PTB7-Th/PC71BM, which has demonstrated >10% PCE via spincoating but only exhibits ~1% PCE when roll-to-roll printed. Of particular interest is the ubiquitous alcohol wash post-treatment applied to the dried active layer, which induces a significant improvement in device performance, and its crucial role for printed films. While it has been speculated that the primary utility of the alcohol post-treatment is to remove the additive 1,8-diiodooctane (DIO) residue in the dried film, we find here that the wash process itself dramatically impacts morphology in printed films regardless of the presence of DIO. Here we employ various x-ray characterization techniques to probe phase separation, crystallinity, and molecular orientation, as well as in-situ grazing-incidence x-ray diffraction (in-situ GIXD) to monitor morphological evolution during the isopropanol post-treatment process. It is discovered that isopropanol induces significant donor polymer alignment and enhanced π-π degree of crystallinity. Through the understanding gained in this study, we are able to achieve a roll-to-roll printed OPV with 5% PCE, which is to our knowledge the highest reported performance for a roll-to-roll printed single junction photoactive layer on a flexible substrate.
The phase separation between donor and acceptor molecules within the active layer of an organic solar cells dictates the morphology and hence is key to the recombination rate and ultimately the performance of the organic solar cell. Molecular dynamics (MD) simulation is a suitable technique to understand this phenomenon; however, conventional all-atom MD simulations cannot reach the appropriate length and time scales to compare with macroscopic observation. Even with the many available coarse-grained MD models, it is difficult to reach these scales. Therefore, we introduce here a 2D compact model to overcome this challenge, built by multiscale coarse-graining. First, we simulate systems including conjugated polymers, fullerenes, and organic solvents using all-atom MD to extract information about molecular conformation and packing. This includes an analysis of polymer solution behavior, fullerene clustering, and binary and tertiary mixing properties. These results are then used to systematically parameterize the molecules used in 2D coarse-grained MD simulations. The 2D simulations probe experimentally relevant length scales that were previously intractable to sample by other MD simulation methods. Using this model, we explore ternary systems including polymer, fullerene, and solvent molecules to investigate the phase separation process between polymer donors and fullerene acceptors. In this scheme, we additionally introduce explicit solvent evaporation to emulate realistic processing conditions. We quantify phase separation domain sizes that are comparable to experimentally observed values from resonant soft x-ray scattering. In addition, we extend this framework to other chemical species to demonstrate the flexibility of the approach.
Group-IV semiconductors have the opportunity to have an equivalent or better temperature coefficient of resistance (TCR) than other microbolometer thermistor materials. By using multiple-quantum-well (MQW) structures, their TCR values can be optimized due to a confinement of carriers. Through two approaches – an activation energy approximation and a custom Monte Carlo transfer matrix method – we simulated this effect for a combination of Group-IV semiconductors and their alloys (e.g., SiGe and GeSn) to find the highest possible TCR, while keeping in mind the critical thicknesses of such layers in a MQW epitaxial stack. We calculated the TCR for a critical-thickness-limited Ge0.8Sn0.2/Ge MQW device to be about -1.9 %/K. Although this TCR is lower than similar SiGe/Si MQW thermistors, GeSn offers possible advantages in terms of fabricating suspended devices with its interesting etch-stop properties shown in previous literature. Furthermore, using finite element modeling of heat transport, we looked at another key bolometer parameter: the thermal time constant. The dimensions of a suspended Ge microbolometer’s supporting legs were fine-tuned for a target response time of 5 ms, incorporating estimations for the size effects of the nanowire-like legs on thermal conductivity.
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