Naphthalenediimide-based n-type polymeric semiconductors are extensively used for constructing high-performance all-polymer solar cells (all-PSCs). For such all-polymer systems, charge recombination can be reduced by using thinner active layers, yet suffering insufficient near-infrared light harvesting from the polymeric acceptor. Conversely, increasing the layer thickness overcomes the light harvesting issue, but at the cost of severe charge recombination effects. Here we demonstrate that to manage light propagation within all-PSCs, a thick bulk-heterojunction film of approximately 350 nm is needed to effectively enhance photo-harvesting in the near-infrared region. To overcome the severe charge recombination in such a thick film, a non-halogenic additive is used to induce a well-ordered micro-structure that inherently suppresses recombination loss. The combined strategies of light management and delicate morphology optimization lead to a promising efficiency over 10% for thick-film all-PSCs with active area of 1 cm2, showing great promise for future large-scale production and application of all-PSCs.

In this work, five PTB7-Th-based conjugated polymers (PTB7-Th, PTBSi20, PTBSi25, PTBSi33, and PTBSi100) with different contents of siloxane-terminated pentyl side chain were synthesized, and properties of corresponding blend films with narrow band gap nonfullerene IEICO-4F acceptor were extensively investigated. According to the contact angle testing, the PTB7-Th with 100% alkyl side chain and PTBSi100 100% siloxane-terminated side chain on the benzodithiophene unit showed surface energy values of 40.04 and 34.52 mJ/m2, respectively. The results demonstrate that relative to alkyl side chain in PTB7-Th, the siloxane-terminated side chain could effectively reduce the surface energy of a resulting polymer. Based on Flory–Huggins interaction parameter estimations, the miscibility between the polymer and IEICO-4F would vary in an order of PTB7-Th > PTBSi20 > PTBSi25 > PTBSi33 > PTBSi100, suggesting that siloxane-terminated side chain would afford a tunable driving force for phase separation. Transmission electron microscopy and Raman mapping could confirm large bulk domains inside the PTBSi100:IEICO-4F blend film. In polymer solar cells, the blend film of the PTBSi100 with the lowest miscibility to IEICO-4F showed an undesirable power conversion efficiency (PCE) of 8.52%, which was significantly lower than that of 11.23% for PTB7-Th, suggesting that too large phase separation driving force is not beneficial for the device performance. Side-chain random copolymers PTBSi20, PTBSi25, and PTBSi33 for fine tuning could display PCEs of 11.94, 12.61, and 11.80%, respectively, all higher than that of PTB7-Th. Our results not only reveal the big surface energy difference between the siloxane-terminated side chain and the common alkyl side chain but also provide a guideline for side chain engineering of conjugated polymer donors with tunable morphology and optimal matching with a nonfullerene acceptor.

The Debye screening length L D is one of the key parameters for the fieldeffect channel geometry. However, to the best of our knowledge, there are little reports on the experimental estimation of L D . In this study, we have reported our recent observation of in situ surface-enhanced Raman scattering (SERS) mapping during the investigation of the operating organic field-effect transistors. Placing SERS enhancers in different positions of the device can obtain charge and potential information at different locations, which can help to analyze the spatial distribution of charge and quantitatively estimate the Debye screening length. The enhancing factor of Raman intensity that is testified somehow increases exponentially with the external electrical field in both experiments and theoretical calculations. The experimental estimated Debye screening length is from 6.5 to 3.6 nm when the gate voltage changed from −30 to −50 V. This value is larger than the traditional consideration that the Debye screening length is less than 1 nm, which is due to the presence of the light field and the corresponding photogenerated carriers distributed in the whole active layer. Besides, the charge trapping effect of SERS enhancers has been testified to introduce weak error during the accumulation mode with large current density. These conditions have well mimicked the working mode of phototransistors, which is of great significance for optimization of phototransistor performance.

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In recently developed organic semiconductors, the continuously improving sample purity makes the stability of the chemical bonds of organic materials themselves become a key factor in device stability, which provides greater uncertainty for the generation of “zeroth defect”, and the spatial resolution of performance at different positions becomes particularly important. In this work, complete maps of electroluminescent, photoluminescent, and Raman scattering in the same area on an organic light-emitting diode during its operation have been achieved with a confocal spectrometer with multiple laser sources. The different spectral characters help to establish different regions and suggest the mechanism of degradation. In particular, Raman scattering has been shown to be very sensitive in a multilayer device to a change in thickness of several nanometers. In amorphous films with few defects, the very weak film uniformity, including the thickness and degree of aggregation, would induce dramatic degradation. The relatively thin and/or loosely textured region easily locally overheats and has the highest probability of “zeroth defect” generation. This method has high spatial resolution, a low level of damage to samples, good reproducibility, and multiple interconnected pieces of information, which is significant for online quality prediction and mechanistic analysis.