Unraveling the Molecular Weight Dependence of High Magnetic Field to Manipulate the Semiconducting Polymer Molecular Orientation.

The magnetic alignment of molecules, which exploits the anisotropy of diamagnetic susceptibility, provides a clean and versatile approach to the structural manipulation of semiconducting polymers. Here, the magnetic-alignment dynamics of two molecular-weight (MW) batches of a diketopyrrolopyrrole (DPP)-based copolymer (PDVT-8) were investigated. Microstructural characterizations revealed that the magnetically aligned, high-MW (Mn = 53.7 kDa) PDVT-8 film exhibited a higher degree of backbone chain alignment and film crystallinity compared with the low-MW (Mn = 17.6 kDa) PDVT-8 film grown via the same magnetic alignment method. We found that as the MW increases, the degree of preaggregation of the polymer molecules in solution significantly increases and the aggregation mode changes from H-aggregation to J-aggregation through a cooperative assembly mechanism. These events improved the responsiveness of high-MW polymer molecules to magnetic fields. Field-effect transistors based on the magnetic aligned high-MW PDVT-8 films exhibited a 6.8-fold increase in hole mobility compared to the spin-coated films, along with a mobility anisotropy ratio of 12.6. This work establishes a significant correlation among chain aggregation behavior in solution, polymer film microstructures, magnetic responsiveness, and carrier transport performance in donor-acceptor polymer systems.

Ultrasmall Cu Nanocrystals Dispersed in Nitrogen-Doped Carbon as Highly Efficient Catalysts for CO2 Electroreduction.

The electroreduction of carbon dioxide (CO2) to a liquid product is a viable method for establishing an artificial carbon cycle. Unfortunately, most electrocatalysts' low efficiency and instability prevent them from being used in practical applications. In the current study, we developed ultrasmall Cu nanocrystals embedded in nitrogen-doped carbon nanosheets (Cu/NC-NSs) for selective CO2 electroreduction by adjusting the potential. Cu/NC-NSs had 43.7 and 63.5% Faradaic efficiencies for the synthesis of ethanol and formate with applied potentials of -0.37 and -0.77 V vs reversible hydrogen electrode (RHE) using a flow cell architecture, respectively. Moreover, these Cu/NC-NSs show a steady catalytic performance up to 16 h. Density functional theory (DFT) calculations were performed to investigate the reaction mechanism. Furthermore, the synergistic effect formed by nitrogen-doped carbon and highly dispersed copper atoms led to their excellent performance in CO2 electroreduction.

Out-of-Plane Alignment of Conjugated Semiconducting Polymers by Horizontal Rotation in a High Magnetic Field.

The effective control of film morphology and molecular packing in the out-of-plane direction of semiconductor polymers plays a critical role in governing charge carrier transport in the direction perpendicular to the substrate. In this study, a highly out-of-plane alignment of the n-type polymer P(NDI2OD-T2) film has been successfully achieved by horizontal rotation in a high magnetic field (HR-HMF). The out-of-plane alignment of the P(NDI2OD-T2) film has showed a change from 72% face-on to 98.2% face-on lamellar texture as well as a 1.6-fold increase of the π-π stacking crystalline correlation length compared with that of as-cast polymer films without HR-HMF-induced alignment. Meanwhile, the film with near-perfect face-on molecular packing exhibited more than 18-fold enhancement of electron mobility compared to the unaligned film. The excellent electrical performance achieved with the HR-HMF process indicates its application potential for fabricating high-performance sandwich-type organic electronic devices, such as solar cells and light-emitting diodes.

Solvent Vapor-Assisted Magnetic Manipulation of Molecular Orientation and Carrier Transport of Semiconducting Polymers.

Effective control of the molecular orientation and the degree of ordering in organic semiconductors is important to achieve high-performance organic electronics. Herein, we have successfully achieved highly oriented films in centimeter scale for a naphthalenedicarboximide-based semiconducting polymer (P(NDI2OD-T2)) by solvent vapor annealing (SVA) of precast films under a high magnetic field (HMF). As revealed by the microstructural studies, the SVA-HMF films exhibit a remarkably higher degree of chain alignment and high morphological uniformity compared to the HMF-guided drop-cast films. Based on the structural evolution of the films with the SVA time, a mechanism is proposed to elucidate the alignment process, which emphasizes that the chain aggregates re-formed in the swollen films trigger magnetic alignment and determine the film order. Compared with the unaligned films, field-effect transistors of the magnetic aligned P(NDI2OD-T2) films have exhibited a 19-fold enhancement of electron mobility and an extraordinarily large mobility anisotropy of 125. Furthermore, a significantly reduced energetic barrier for activated transport is observed on the aligned devices from temperature-variable measurements. The improved performance achieved by the HMF-SVA process has indicated its potential for high-performance organic electronic applications.

Solution-processed solar cells based on inorganic bulk heterojunctions with evident hole contribution to photocurrent generation.

To develop solution-processed and novel device structures is of great importance for achieving advanced and low-cost solar cells. In this paper, we report the solution-processed solar cells based on inorganic bulk heterojunctions (BHJs) featuring a bulk crystalline Sb2S3 absorbing layer interdigitated with a TiO2 nanoarray as an electron transporter. A solution-processed amorphous-to-crystalline transformation strategy is used for the preparation of Sb2S3/TiO2-BHJs. Steady-state and dynamic results demonstrate that the crystalline structure in the Sb2S3 absorbing layer is crucial for efficient devices, and a better Sb2S3 crystallization favors a higher device performance by increasing the charge collection efficiency for a higher short-circuit current, due to reduced interfacial and bulk charge recombinations, and enhancing the open-circuit voltage and fill factor with the reduced defect states in the Sb2S3 layer as well. Moreover, an evident contribution to photocurrent generation from the photogenerated holes in the Sb2S3 layer is revealed by experimental and simulated dynamic data. These results imply a kind of potential non-excitonic BHJ for energy conversion.