Surpassing 10% Efficiency Benchmark for Nonfullerene Organic Solar Cells by Scalable Coating in Air from Single Nonhalogenated Solvent

The commercialization of nonfullerene organic solar cells (OSCs) critically relies on the response under typical operating conditions (for instance, temperature and humidity) and the ability of scale‐up. Despite the rapid increase in power conversion efficiency (PCE) of spin‐coated devices fabricated in a protective atmosphere, the efficiencies of printed nonfullerene OSC devices by blade coating are still lower than 6%. This slow progress significantly limits the practical printing of high‐performance nonfullerene OSCs. Here, a new and relatively stable nonfullerene combination is introduced by pairing the nonfluorinated acceptor IT‐M with the polymeric donor FTAZ. Over 12% efficiency can be achieved in spin‐coated FTAZ:IT‐M devices using a single halogen‐free solvent. More importantly, chlorine‐free, blade coating of FTAZ:IT‐M in air is able to yield a PCE of nearly 11% despite a humidity of ≈50%. X‐ray scattering results reveal that large π–π coherence length, high degree of face‐on orientation with respect to the substrate, and small domain spacing of ≈20 nm are closely correlated with such high device performance. The material system and approach yield the highest reported performance for nonfullerene OSC devices by a coating technique approximating scalable fabrication methods and hold great promise for the development of low‐cost, low‐toxicity, and high‐efficiency OSCs by high‐throughput production.     

Achieving Highly Efficient Nonfullerene Organic Solar Cells with Improved Intermolecular Interaction and Open‐Circuit Voltage

A new acceptor–donor–acceptor‐structured nonfullerene acceptor ITCC (3,9‐bis(4‐(1,1‐dicyanomethylene)‐3‐methylene‐2‐oxo‐cyclopenta[b]thiophen)‐5,5,11,11‐tetrakis(4‐hexylphenyl)‐dithieno[2,3‐d′:2,3‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]‐dithiophene) is designed and synthesized via simple end‐group modification. ITCC shows improved electron‐transport properties and a high‐lying lowest unoccupied molecular orbital level. A power conversion efficiency of 11.4% with an impressive V _OC of over 1 V is recorded in photovoltaic devices, suggesting that ITCC has great potential for applications in tandem organic solar cells.     

Evolution of the nanomorphology of photovoltaic polyfluorene blends: sub-100 nm resolution with x-ray spectromicroscopy

We investigate the influence of annealing on the morphology of intimately mixed blends of the conjugated polymers poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylene-diamine) (PFB) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT) with scanning transmission x-ray microscopy (STXM). Through the use of a zone plate with theoretical Rayleigh resolution of 30?nm, we are able to resolve sub-100?nm bulk structure in these films. Surprisingly, for unannealed films spin-coated from chloroform we observe features with an average diameter of 85?nm. The high degree of photoluminescence quenching in these as-spun films (>95%) implies that there is significant intermixing within the 85?nm structures, indicating that a hierarchy of phase separation exists even on the length scale of less than 100?nm. With annealing up to 160?°C, close to the T(g) of the components, there is little change in the feature sizes observed by STXM, although an increase in variation of the composition is observed. With annealing above 160?°C the imaged features begin to evolve in size, increasing to 225?nm in extent, alongside large changes in composition with annealing to 200?°C. Comparing the evolution of morphology imaged by STXM with the change in photoluminescence quenching with annealing, we propose that phase separation first evolves via the evolution of relatively pure phases on the length scale of a few to tens of nanometres within the larger 85?nm structures. Once the length scale of compositional fluctuations exceeds 85?nm (for anneal temperatures above 160?°C) the hierarchy of phase separation is lost and the subsequent morphological evolution is readily imaged by STXM. Applying the results of an exciton diffusion and quenching model, we find good agreement between the size of the domains measured by STXM (above 180?°C) and the results of the model for an exciton diffusion length of 15?nm. The growth in domain size and towards purer structures has also been observed with resonant soft x-ray scattering.     

Algorithmic stability and sanity-check bounds for leave-one-out cross-validation.

In this article we prove sanity-check bounds for the error of the leave-one-out cross-validation estimate of the generalization error: that is, bounds showing that the worst-case error of this estimate is not much worse than that of the training error estimate. The name sanity check refers to the fact that although we often expect the leave-one-out estimate to perform considerably better than the training error estimate, we are here only seeking assurance that its performance will not be considerably worse. Perhaps surprisingly, such assurance has been given only for limited cases in the prior literature on cross-validation. Any nontrivial bound on the error of leave-one-out must rely on some notion of algorithmic stability. Previous bounds relied on the rather strong notion of hypothesis stability, whose application was primarily limited to nearest-neighbor and other local algorithms. Here we introduce the new and weaker notion of error stability and apply it to obtain sanity-check bounds for leave-one-out for other classes of learning algorithms, including training error minimization procedures and Bayesian algorithms. We also provide lower bounds demonstrating the necessity of some form of error stability for proving bounds on the error of the leave-one-out estimate, and the fact that for training error minimization algorithms, in the worst case such bounds must still depend on the Vapnik-Chervonenkis dimension of the hypothesis class.     

Formation of Nanocrystalline Silicon Carbide Powder from Chlorine-Containing Polycarbosilane Precursors

Nanocrystalline ß-SiC particulates with a grain-size range of 5-20 nm were prepared by heating a prepyrolyzed, chlorine-containing polysilane/polycarbosilane (PS/PCS) to 1600°C. The transformation from the prepyrolyzed PS/PCS to nanocrystalline SiC was investigated by differential thermal analysis, thermogravimetric analysis, X-ray diffractometry, mass spectrometry, and infrared spectroscopy. The results indicated that the nanocrystalline ß-SiC was formed by the crystallization of the PS/PCS random network and the crosslinking of Si-Si, Si-Cl, and Si-CH₂-Si bonds. Transmission electron microscopy observation showed that SiC particulates consisted of equiaxed, randomly oriented, ultrafine grains.     

Revealing the Impact of F4‐TCNQ as Additive on Morphology and Performance of High‐Efficiency Nonfullerene Organic Solar Cells

Fluorinated molecule 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4‐TCNQ) and its derivatives have been used in polymer:fullerene solar cells primarily as a dopant to optimize the electrical properties and device performance. However, the underlying mechanism and generality of how F4‐TCNQ affects device operation and possibly the morphology is poorly understood, particularly for emerging nonfullerene organic solar cells. In this work, the influence of F4‐TCNQ on the blend film morphology and photovoltaic performance of nonfullerene solar cells processed by a single halogen‐free solvent is systematically investigated using a set of morphological and electrical characterizations. In solar cells with a high‐performance polymer:small molecule blend FTAZ:IT‐M, F4‐TCNQ has a negligibly small effect on the molecular packing and surface characteristics, while it clearly affects the electronic properties and mean‐square composition variation of the bulk. In comparison to the control devices with an average power conversion efficiency (PCE) of 11.8%, inclusion of a trace amount of F4‐TCNQ in the active layer has improved device fill factor and current density, which has resulted into a PCE of 12.4%. Further increase in F4‐TCNQ content degrades device performance. This investigation aims at delineating the precise role of F4‐TCNQ in nonfullerene bulk heterojunction films, and thereby establishing a facile approach to fabricate highly optimized nonfullerene solar cells.     

Near-Optimal Reinforcement Learning in Polynomial Time

We present new algorithms for reinforcement learning and prove that they have polynomial bounds on the resources required to achieve near-optimal return in general Markov decision processes. After observing that the number of actions required to approach the optimal return is lower bounded by the mixing time T of the optimal policy (in the undiscounted case) or by the horizon time T (in the discounted case), we then give algorithms requiring a number of actions and total computation time that are only polynomial in T and the number of states and actions, for both the undiscounted and discounted cases. An interesting aspect of our algorithms is their explicit handling of the Exploration-Exploitation trade-off.