The importance of morphology to organic solar cell performance is well known, but to date, the lack of quantitative, nanoscale and statistical morphological information has hindered obtaining direct links to device function. Here resonant X‐ray scattering and microscopy are combined to quantitatively measure the nanoscale domain size, distribution and composition in high efficiency solar cells based on PTB7 and PC71BM. The results show that the solvent additive diiodooctane dramatically shrinks the domain size of pure fullerene agglomerates that are embedded in a polymer‐rich 70/30 wt.% molecularly mixed matrix, while preserving the domain composition relative to additive‐free devices. The fundamental miscibility between the species – measured to be equal to the device's matrix composition – is likely the dominant factor behind the overall morphology with the additive affecting the dispersion of excess fullerene. As even the molecular ordering measured by X‐ray diffraction is unchanged between the two processing routes the change in the distribution of domain size and therefore increased domain interface is primarily responsible for the dramatic increase in device performance. While fullerene exciton harvesting is clearly one significant cause of the increase owing to smaller domains, a measured increase in harvesting from the polymer species indicates that the molecular mixing is not the reason for the high efficiency in this system. Rather, excitations in the polymer likely require proximity to a pure fullerene phase for efficient charge separation and transport. Furthermore, in contrast to previous measurements on a PTB7‐based system, a hierarchical morphology was not observed, indicating that it is not necessary for high performance.

The device function of polymer bulk heterojunction (BHJ) solar cells has been commonly interpreted to arise from charge separation at discrete interfaces between phase-separated materials and subsequent charge transport through these phases without consideration of phase purity. To probe composition, the miscibility of poly(3-hexylthiophene) (P3HT) and poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene) (MDMO-PPV) with phenyl-C61-butyric acid methyl ester (PCBM) has been determined, while the effects of polymer crystallinity on miscibility are probed using P3HT grades of varying regioregularity. It is found that, while no intercalation occurs in P3HT crystals, amorphous portions of P3HT and MDMO-PPV contain significant concentrations of PCBM, calling into question models based on pure phases and discrete interfaces. Furthermore, depth profiles of P3HT/PCBM bilayers reveal that even short annealing causes significant interdiffusion of both materials, showing that under no conditions do pure amorphous phases exist in BHJ or annealed bilayer devices. These results suggest that current models of charge separation and transport must be refined.

Band-like charge transport is observed in lead halide perovskite field-effect transistors.

No abstract

High-mobility semiconducting polymers offer the opportunity to develop flexible and large-area electronics for several applications, including wearable, portable and distributed sensors, monitoring and actuating devices. An enabler of this technology is a scalable printing process achieving uniform electrical performances over large area. As opposed to the deposition of highly crystalline films, orientational alignment of polymer chains, albeit commonly achieved by non-scalable/slow bulk alignment schemes, is a more robust approach towards large-area electronics. By combining pre-aggregating solvents for formulating the semiconductor and by adopting a room temperature wired bar-coating technique, here we demonstrate the fast deposition of submonolayers and nanostructured films of a model electron-transporting polymer. Our approach enables directional self-assembling of polymer chains exhibiting large transport anisotropy and a mobility up to 6.4 cm2 V−1 s−1, allowing very simple device architectures to operate at 3.3 MHz. Thus, the proposed deposition strategy is exceptionally promising for mass manufacturing of high-performance polymer circuits.

Molecular orientation critically influences the mechanical, chemical, optical and electronic properties of organic materials. So far, molecular-scale ordering in soft matter could be characterized with X-ray or electron microscopy techniques only if the sample exhibited sufficient crystallinity. Here, we show that the resonant scattering of polarized soft X-rays (P-SoXS) by molecular orbitals is not limited by crystallinity and that it can be used to probe molecular orientation down to size scales of 10 nm. We first apply the technique on highly crystalline small-molecule thin films and subsequently use its high sensitivity to probe the impact of liquid-crystalline ordering on charge mobility in polymeric transistors. P-SoXS also reveals scattering anisotropy in amorphous domains of all-polymer organic solar cells where interfacial interactions pattern orientational alignment in the matrix phase, which probably plays an important role in the photophysics. The energy and q-dependence of the scattering anisotropy allows the identification of the composition and the degree of orientational order in the domains.

Substituted side chains are fundamental units in solution processable organic semiconductors in order to achieve a balance of close intermolecular stacking, high crystallinity, and good compatibility with different wet techniques. Based on four air-stable solution-processed naphthalene diimides fused with 2-(1,3-dithiol-2-ylidene)malononitrile groups (NDI-DTYM2) that bear branched alkyl chains with varied side-chain length and different branching position, we have carried out systematic studies on the relationship between film microstructure and charge transport in their organic thin-film transistors (OTFTs). In particular synchrotron measurements (grazing incidence X-ray diffraction and near-edge X-ray absorption fine structure) are combined with device optimization studies to probe the interplay between molecular structure, molecular packing, and OTFT mobility. It is found that the side-chain length has a moderate influence on thin-film microstructure but leads to only limited changes in OTFT performance. In contrast, the position of branching point results in subtle, yet critical changes in molecular packing and leads to dramatic differences in electron mobility ranging from ~0.001 to >3.0 cm(2) V(-1) s(-1). Incorporating a NDI-DTYM2 core with three-branched N-alkyl substituents of C(11,6) results in a dense in-plane molecular packing with an unit cell area of 127 Å(2), larger domain sizes of up to 1000 × 3000 nm(2), and an electron mobility of up to 3.50 cm(2) V(-1) s(-1), which is an unprecedented value for ambient stable n-channel solution-processed OTFTs reported to date. These results demonstrate that variation of the alkyl chain branching point is a powerful strategy for tuning of molecular packing to enable high charge transport mobilities.

The development of nonfullerene acceptors (NFAs), which are used to replace fullerene derivatives in organic solar cells (OSCs) due to their extended light absorption and tunable energy levels, has seen impressive progress in the past few years. [1][2][3][4] A range of new NFAs with different building blocks and geometrical dimensions has been designed to boost the power conversion efficiency (PCE) of OSCs. Among the highest performing NFAs, linear rod-like acceptor-donor-acceptor (A-D-A) structures incorporating fused ladder-type aromatics have attracted much interest. Common donor units include 4,9-dihydro-s-indaceno[1,2-b:5,6-b′]dithiophene (IDT) [5][6][7][8][9] and 6,12-dihydro-dithienoindeno [10][11][12][13][14][15][16][17][18] In both cases, the fused core facilitates π-electron delocalization and improves the π-π stacking between molecules, hence enhancing the intrinsic charge carrier mobility.In 2015, Zhan and coworkers reported a new NFA, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11--b′]dithiophene (ITIC) (Scheme 1), which is comprised an electron-donating IDTT-based core flanked by two electron-withdrawing units of 1,1-dicyanomethylene-3-indanone (IC), that exhibited a promising PCE of 6.8% at that time. [10] Since then, many strategies have been applied to modify the structure of ITIC in order to adjust the absorption spectra and energy levels to further improve the PCE, for example, by changing the side chains, [17,18] extending the conjugation length, [19][20][21][22] and substituting the end acceptor groups. [13][14][15][16] To date, a few systems based on these NFAs have achieved a PCE of over 10%. [5,[13][14][15]18,20,22] However, it is noticeable that in all cases these NFAs incorporate phenylalkyl or thienylalkyl side chains as the solubilizing groups on the fused core. These aryl-based side chains facilitate the synthesis of the IDTT core under Friedel-Crafts conditions via the formation of stable triaryl cations. However, since the nature of the side chains has a