Topology sorting: Separating linear/star polymer blend components by imbibition in nanopores.

We report the imbibition and adsorption kinetics of a series of symmetric linear/star cis-1,4-polyisoprene blends within the long channels of self-ordered nanoporous anodic aluminum oxide (abbreviated: AAO). Using in situ nanodielectric spectroscopy, we followed the evolution of the longest chain modes in the blends with a judicious selection of molar masses for the constituent components. We demonstrated differences in the imbibition kinetics of linear and star components based on the relative viscosities (e.g., polymers with lower zero-shear viscosity penetrated first the nanopores). Following the complete imbibition of the pores, the adsorption time, τads, of each component was evaluated from the reduction in the dielectric strength of the respective chain modes. In the majority of blends, both components exhibited slower adsorption kinetics with respect to the homopolymers. The only exception was the case of entangled stars mixed with shorter linear chains, the latter acting as a diluent for the star component. This gives rise to what is known as topology sorting, e.g., the separation of linear/star blend components in the absence of solvent. Moreover, a simple relation (τads ∼ 10 × tpeak; tpeak is the time needed for the complete filling of pores) was found for linear polymers and stars. This suggested that the characteristic timescale of imbibition (tpeak) governs the adsorption process of polymers. It further implied the possibility of predicting the adsorption times of high molar mass polymers of various architectures by the shorter imbibition times.

Enhanced sub-1 eV detection in organic photodetectors through tuning polymer energetics and microstructure.

One of the key challenges facing organic photodiodes (OPDs) is increasing the detection into the infrared region. Organic semiconductor polymers provide a platform for tuning the bandgap and optoelectronic response to go beyond the traditional 1000-nanometer benchmark. In this work, we present a near-infrared (NIR) polymer with absorption up to 1500 nanometers. The polymer-based OPD delivers a high specific detectivity D* of 1.03 × 1010 Jones (-2 volts) at 1200 nanometers and a dark current Jd of just 2.3 × 10-6 ampere per square centimeter at -2 volts. We demonstrate a strong improvement of all OPD metrics in the NIR region compared to previously reported NIR OPD due to the enhanced crystallinity and optimized energy alignment, which leads to reduced charge recombination. The high D* value in the 1100-to-1300-nanometer region is particularly promising for biosensing applications. We demonstrate the OPD as a pulse oximeter under NIR illumination, delivering heart rate and blood oxygen saturation readings in real time without signal amplification.

Infrared Organic Photodetectors Employing Ultralow Bandgap Polymer and Non-Fullerene Acceptors for Biometric Monitoring.

Recent efforts in the field of organic photodetectors (OPD) have been focused on extending broadband detection into the near-infrared (NIR) region. Here, two blends of an ultralow bandgap push-pull polymer TQ-T combined with state-of-the-art non-fullerene acceptors, IEICO-4F and Y6, are compared to obtain OPDs for sensing in the NIR beyond 1100 nm, which is the cut off for benchmark Si photodiodes. It is observed that the TQ-T:IEICO-4F device has a superior IR responsivity (0.03 AW-1 at 1200 nm and -2 V bias) and can detect infrared light up to 1800 nm, while the TQ-T:Y6 blend shows a lower responsivity of 0.01 AW-1 . Device physics analyses are tied with spectroscopic and morphological studies to link the superior performance of TQ-T:IEICO-4F OPD to its faster charge separation as well as more favorable donor-acceptor domains mixing. In the polymer blend with Y6, the formation of large agglomerates that exceed the exciton diffusion length, which leads to high charge recombination, is observed. An application of these devices as biometric sensors for real-time heart rate monitoring via photoplethysmography, utilizing infrared light, is demonstrated.

Highly Efficient Indoor Organic Solar Cells by Voltage Loss Minimization through Fine-Tuning of Polymer Structures.

Herein, we report a detailed study on the optoelectronic properties, photovoltaic performance, structural conformation, morphology variation, charge carrier mobility, and recombination dynamics in bulk heterojunction solar cells comprising a series of donor-acceptor conjugated polymers as electron donors based on benzodithiophene (BDT) and 5,8-bis(5-bromothiophen-2-yl)-6,7-difluoro-2,3-bis(3-(octyloxy)phenyl)quinoxaline as a function of the BDT's thienyl substitution (alkyl (WF3), alkylthio (WF3S), and fluoro (WF3F)). The synergistic positive effects of the fluorine substituents on the minimization of the bimolecular recombination losses, the reduction of the series resistances (RS), the increment of the shunt resistances (RSh), the suppression of the trap-assisted recombination losses, the balanced charge transport, the finer nanoscale morphology, and the deeper highest occupied molecular orbital (EHOMO) are manifested versus the alkyl and alkylthio substituents. According to these findings, the WF3F:[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM)-based organic photovoltaic device is a rare example that features a high power conversion efficiency (PCE) of 17.34% under 500 lx indoor light-emitting diode light source with a high open-circuit voltage (VOC) of 0.69 V, due to the suppression of the voltage losses, and a PCE of 9.44% at 1 sun (100 mW/cm2) conditions, simultaneously.