Microphase-separated block copolymers composed of electron donor and acceptor blocks may provide morphology control to address many challenges in organic electronics. Crucial to controlling the self-assembly of fully conjugated block copolymers is tuning the interplay between crystallization of the individual blocks and microphase separation between the donor and the acceptor. Thus, we have examined the kinetics of the morphological evolution in P3HT-b-PFTBT block copolymer films during two processes: solution casting and thermal annealing. We use in situ wide-angle and small-angle grazing incidence X-ray scattering to monitor the crystallization of P3HT and microphase separation between the two blocks. We find that during film drying, initial P3HT crystallization happens quickly, before phase separation of the two blocks. However, crystallization is significantly suppressed with respect to neat materials, enabling microphase separation to proceed at time scales after some initial crystallization of the donor block takes place. This enables a mesoscale structure to develop during processes such as thermal annealing because self-assembly of the lamellar structure takes place before the crystallization of the donor block is complete. We also find that significant crystallization of PFTBT blocks after P3HT crystallization is possible at elevated temperatures. Crystallization of both blocks is important to maximize the performance of solar cells and transistors with block copolymer active layers. As a consequence, we exceed 3% average power conversion efficiencies in P3HT-b-PFTBT photovoltaic devices.
A comprehensive experimental study was conducted on the dealloying of PdNi6 nanoparticles under various conditions. A two-stage dealloying protocol was developed to leach >95% of Ni while minimizing the dissolution of Pd. The final structure of the dealloyed particle was strongly dependent on the acid used and temperature. When H2SO4 and HNO3 solutions were used in the first stage of dealloying, solid and porous particles were generated, respectively. The porous particles have a 3-fold higher electrochemical surface area per Pd mass than the solid ones. The dealloyed PdNi6 nanoparticles were then used as a core material for the synthesis of core–shell catalysts. These catalysts were synthesized in gram-size batches and involved Pt displacement of an underpotentially deposited (UPD) Cu monolayer. The resulting materials were characterized by scanning transmission electron microscopy (STEM) and in situ X-ray diffraction (XRD). The oxygen reduction reaction (ORR) activity of the core–shell catalysts is 7-fold higher than the state-of-the-art Pt/C. The high activity was confirmed by a more than 40 mV improvement in fuel cell performance with a Pt loading of 0.1 mg cm−2 by using the core–shell catalysts.
Ceramic anodes comprising infiltrated in porous ytttria-stabilized zirconia were investigated. Upon reduction at , the electronically insulating phase transformed to , which has a bulk electronic conductivity of under fuel cell conditions. An anode conductivity of was achieved with a low loading of of the total anode. The infiltrated composite is dimensionally stable upon redox cycling, and a Pd catalyst was required to achieve good fuel cell performance. Fuel cell performance with methane was lower than with hydrogen. This lower methane performance could be due to coking.
Several recent reports have demonstrated that fluorinated analogues of donor/acceptor copolymers surpass nonfluorinated counterparts in terms of performance in electronic devices. Using a copolymer series consisting of fluorinated, partially fluorinated, and nonfluorinated benzotriazole, we confirm that the addition of fluorine substituents beneficially impacts charge transport in polymer semiconductors. Transistor measurements demonstrated a factor of 5 increase in carrier mobilities with the degree of fluorination of the backbone. Furthermore, grazing-incidence X-ray diffraction data indicates progressively closer packing between the conjugated cores and an overall greater amount of π-stacking in the fluorinated materials. It is likely that attractive interactions between the electron-rich donor and fluorinated electron-deficient acceptor units induce very tightly stacking crystallites, which reduce the energetic barrier for charge hopping. In addition, a change in crystallite orientation was observed from primarily edge-on without fluorine substituents to mostly face-on with fluorinated benzotriazole.
'/%3e%3cuse xlink:href='%23a' transform='rotate(23.036 .093 25.536)'/%3e%3cuse xlink:href='%23a' transform='rotate(45.87 1.273 16.18)'/%3e%3cuse xlink:href='%23a' transform='rotate(69.945 .996 12.078)'/%3e%3cuse xlink:href='%23a' transform='rotate(20.66 -19.689 31.932)'/%3e%3c/svg%3e)
'/%3e%3c/defs%3e%3cpath fill='%23012169' d='M0 0h10080v5040H0z'/%3e%3cpath stroke='%23fff' stroke-width='.6' d='m0 0 6 3m0-3L0 3' clip-path='url(%23b)' transform='scale(840)'/%3e%3cpath stroke='%23e4002b' stroke-width='.4' d='m0 0 6 3m0-3L0 3' clip-path='url(%23c)' transform='scale(840)'/%3e%3cpath stroke='%23fff' stroke-width='840' d='M2520 0v2520M0 1260h5040'/%3e%3cpath stroke='%23e4002b' stroke-width='504' d='M2520 0v2520M0 1260h5040'/%3e%3cg fill='%23fff'%3e%3cuse xlink:href='%23d' x='2520' y='3780'/%3e%3cuse xlink:href='%23a' x='7560' y='4200'/%3e%3cuse xlink:href='%23a' x='6300' y='2205'/%3e%3cuse xlink:href='%23a' x='7560' y='840'/%3e%3cuse xlink:href='%23a' x='8680' y='1869'/%3e%3cuse xlink:href='%23e' x='8064' y='2730'/%3e%3c/g%3e%3c/svg%3e)
'%3e%3cpath fill='%23012169' d='M0 0v30h60V0z'/%3e%3cpath stroke='%23fff' stroke-width='6' d='m0 0 60 30m0-30L0 30'/%3e%3cpath stroke='%23C8102E' stroke-width='4' d='m0 0 60 30m0-30L0 30' clip-path='url(%23b)'/%3e%3cpath stroke='%23fff' stroke-width='10' d='M30 0v30M0 15h60'/%3e%3cpath stroke='%23C8102E' stroke-width='6' d='M30 0v30M0 15h60'/%3e%3c/g%3e%3c/svg%3e)