A new strategy for enhancing the photoinduced mechanical force is demonstrated using a reprocessable azobenzene-containing liquid crystalline network (LCN). The basic idea is to store mechanical strain energy in the polymer beforehand so that UV light can then be used to generate a mechanical force not only from the direct light to mechanical energy conversion upon the trans-cis photoisomerization of azobenzene mesogens but also from the light-triggered release of the prestored strain energy. It is shown that the two mechanisms can add up to result in unprecedented photoindued mechanical force. Together with the malleability of the polymer stemming from the use of dynamic covalent bonds for chain crosslinking, large-size polymer photoactuators in the form of wheels or spring-like "motors" can be constructed, and, by adjusting the amount of prestored strain energy in the polymer, a variety of robust, light-driven motions with tunable rolling or moving direction and speed can be achieved. The approach of prestoring a controllable amount of strain energy to obtain a strong and tunable photoinduced mechanical force in azobenzene LCN can be further explored for applications of light-driven polymer actuators.
As a prototype tool for slot‐die coating, blade‐coating exhibits excellent compatibility with large‐area roll‐to‐roll coating. A ternary organic solar cell based on PBDB‐T:PTB7‐Th:FOIC blends is fabricated by blade‐coating and exhibits a power conversion efficiency of 12.02%, which is one of the highest values for the printed organic solar cells in ambient environment. It is demonstrated that blade‐coating can enhance crystallization of these three materials, but the degree of induction is different (FOIC > PBDB‐T > PTB7‐Th). Thus, the blade‐coated PBDB‐T:FOIC device presents much higher electron mobility than hole mobility due to the very high crystallinity of FOIC. Upon the addition of PTB7‐Th into the blade‐coated PBDB‐T:FOIC blends, the crystallinity of FOIC decreases together with the corresponding electron mobility, due to the better miscibility between PTB7‐Th and FOIC. The ternary strategy not only maintains the well‐matched crystallinity and mobilities, but also increases the photocurrent with complementary light absorption as well as the Förster resonant energy transfer. Furthermore, small domains with homogeneously distributed nanofibers are observed in favor of the exciton dissociation and charge transport. This combination of blade‐coating and ternary strategies exhibits excellent synergistic effect in optimizing morphology, showing great potential in the large‐area fabrication of highly efficient organic solar cells.
For some thermosensitive polymers, the absence of an upper critical solution temperature (UCST) in water in an accessible temperature range (say, 5−90 °C) can be attributed to the influence of charged groups in the polymer structure. This property was exploited in the present study to achieve ultrasensitive pH-induced water solubility switch of UCST polymers in physiological medium. By incorporating either acrylic acid (AAc) or 4-vinylpyridine (4VP) comonomer units in the random copolymer of acrylamide and acrylonitrile (P(AAm-co-AN-co-AAc) or P(AAm-co-AN-co-4VP)), the pHinduced shift of UCST was investigated by monitoring the solution cloud point. The results revealed an unusually large shift of the cloud point upon pH variation over a small range. In particular, one P(AAm-co-AN-co-4VP) sample exhibited a cloud point drop from 72 °C at pH 4.75 to 15 °C at pH 4.50 (i.e., 57 K shift over 0.25 pH units), and its transition from soluble to insoluble state at room temperature was visually observable over a pH change as little as 0.05 unit. Using this sample as macromolecular chain transfer agent to polymerize dimethylacrylamide (DMA) through RAFT, an ABA-type triblock copolymer of P(AAm-co-AN-co-4VP)-b-PDMA-b-P(AAm-co-AN-co-4VP) was obtained, and it showed an even larger cloud point switch from 71 to 10 °C with pH decreasing from 4.75 to 4.50. Consequently, the micelle formed by this block copolymer was stable at 37 °C with pH from 7.00 down to 4.75 but abruptly dissolved at pH 4.50 due to the water solubility switch. This study demonstrates a new UCST polymer-based approach to polymer assemblies that can sense a very small pH change by undergoing straightforward water solubility switch.
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