Polymerized Thermally Activated Delayed-Fluorescence Small Molecules: Long-Axis Polymerization Leads to a Nearly Concentration-Independent Luminescence.

Nowadays numerous thermally activated delayed fluorescence (TADF) polymers have been developed for PLEDs to realize high device performance and tunable emission colors. However, they often possess a strong concentration dependence on their luminescence including aggregation-caused quenching (ACQ) and aggregation-induced emission (AIE). Herein, we first report a nearly concentration-independent TADF polymer based on the strategy of polymerized TADF small molecules. It is found that when a donor-acceptor-donor (D-A-D) type TADF small molecule is polymerized through its long-axis direction, the triplet state is distributed along the polymeric backbone to effectively suppress the unwanted concentration quenching. Unlike the short-axis one with an ACQ effect, the photoluminescent quantum yield (PLQY) of the resultant long-axis polymer remains almost unchanged with the increasing doping concentration. Accordingly, a promising external quantum efficiency (EQE) up to 20 % is successfully achieved in a whole doping control window of 5-100 wt. %.

Stretchable and Self-Adhesive PEDOT:PSS Blend with High Sweat Tolerance as Conformal Biopotential Dry Electrodes.

Dry epidermal electrodes that can always form conformal contact with skin can be used for continuous long-term biopotential monitoring, which can provide vital information for disease diagnosis and rehabilitation. But, this application has been limited by the poor contact of dry electrodes on wet skin. Herein, we report a biocompatible fully organic dry electrode that can form conformal contact with both dry and wet skin even during physical movement. The dry electrodes are prepared by drop casting an aqueous solution consisting of poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS), poly(vinyl alcohol) (PVA), tannic acid (TA), and ethylene glycol (EG). The electrodes can exhibit a conductivity of 122 S cm-1 and a mechanical stretchability of 54%. Moreover, they are self-adhesive to not only dry skin but also wet skin. As a result, they can exhibit a lower contact impedance to skin than commercial Ag/AgCl gel electrodes on both dry and sweat skins. They can be used as dry epidermal electrodes to accurately detect biopotential signals including electrocardiogram (ECG) and electromyogram (EMG) on both dry and wet skins for the users at rest or during physical movement. This is the first time to demonstrate dry epidermal electrodes self-adhesive to wet skin for accurate biopotential detection.

Sterically-Locked Donor-Acceptor Conjugated Polymers Showing Efficient Thermally Activated Delayed Fluorescence.

Donor-acceptor (D-A) conjugated polymers often possess a significant frontier molecular orbital overlap because of the conjugation elongation, leading to no thermally activated delayed fluorescence (TADF) caused by a large singlet-triplet energy splitting (▵EST ). Herein a novel steric locking strategy is proposed by incorporating methyl groups into D-A conjugated polymers. Benefitting from the methyl hindrance, the torsion between the donor and acceptor can be well tuned to form a sterically-locked conformation, so that the unwanted relaxation toward planarity and thus conjugation elongation is prevented to boost hole-electron separation. The resultant D-A conjugated polymer achieves an extremely low ΔEST of 0.09 eV to enable efficient TADF. The corresponding doped and non-doped devices are fabricated via a solution process, revealing a record-high external quantum efficiency (EQE) of 24.0 % (79.4 cd A-1 , 75.0 lm W-1 ) and 15.3 % (50.9 cd A-1 , 47.3 lm W-1 ).

Meta Junction Promoting Efficient Thermally Activated Delayed Fluorescence in Donor-Acceptor Conjugated Polymers.

The meta junction is proposed to realize efficient thermally activated delayed fluorescence (TADF) in donor-acceptor (D-A) conjugated polymers. Based on triphenylamine as D and dicyanobenzene as A, as a proof of concept, a series of D-A conjugated polymers has been developed by changing their connection sites. When the junction between D and A is tuned from para to meta, the singlet-triplet energy splitting (ΔEST ) is found to be significantly decreased from 0.44 to 0.10 eV because of the increasing hole-electron separation. Unlike the para-linked analogue with no TADF, consequently, the meta-linked polymer shows a strong delayed fluorescence. Its corresponding solution-processed organic light-emitting diodes (OLEDs) achieve a promising external quantum efficiency (EQE) of 15.4 % (51.9 cd A-1 , 50.9 lm W-1 ) and CIE coordinates of (0.34, 0.57). The results highlight the bright future of D-A conjugated polymers used for TADF OLEDs.

Bridging Small Molecules to Conjugated Polymers: Efficient Thermally Activated Delayed Fluorescence with a Methyl-Substituted Phenylene Linker.

Based on a "TADF + Linker" strategy (TADF=thermally activated delayed fluorescence), demonstrated here is the successful construction of conjugated polymers that allow highly efficient delayed fluorescence. Small molecular TADF blocks are linked together using a methyl-substituted phenylene linker to form polymers. With the growing number of methyl groups on the phenylene, the energy level of the local excited triplet state (3 LEb ) from the delocalized polymer backbone gradually increases, and finally surpasses the charge-transfer triplet state (3 CT). As a result, the diminished delayed fluorescence can be recovered for the tetramethyl phenylene containing polymer, revealing a record-high external quantum efficiency (EQE) of 23.5 % (68.8 cd A-1 , 60.0 lm W-1 ) and Commission Internationale de l'Eclairage (CIE) coordinates of (0.25, 0.52). Combined with an orange-red TADF emitter, a bright white electroluminescence is also obtained with a peak EQE of 20.9 % (61.1 cd A-1 , 56.4 lm W-1 ) and CIE coordinates of (0.36, 0.51).

Achieving Deep-Blue Thermally Activated Delayed Fluorescence in Nondoped Organic Light-Emitting Diodes through a Spiro-Blocking Strategy.

A deep-blue thermally activated delayed fluorescence (TADF) emitter TXADO-spiro-DMACF has been reported for nondoped organic light-emitting diodes (OLEDs) by integrating an appropriate blocking unit with the donor (D)-acceptor (A)-donor (D)-type TADF emitter via a spiro linkage. Benefiting from the characteristic perpendicular arrangement, the intermolecular interactions are expected to be weakened to some degree. As a result, TXADO-spiro-DMACF shows a very small bathochromic shift of 8 nm associated with a narrowed full width at half maximum of 54 nm on going from solution to the film. The corresponding nondoped device successfully achieves a bright deep-blue emission, revealing Commission Internationale de l'Eclairage coordinates of (0.16, 0.09) and a peak external quantum efficiency of 5.3% (5.3 cd/A, 5.9 lm/W). The results clearly indicate that spiro-blocking is a promising strategy to develop deep-blue TADF emitters capable of nondoped OLEDs.

Teaching an Old Poly(arylene ether) New Tricks: Efficient Blue Thermally Activated Delayed Fluorescence.

Polymer light-emitting diodes are attractive for optoelectronic applications owing to their brightness and ease of processing. However, often metals have to be inserted to increase the luminescence efficiency, and producing blue emitters is a challenge. Here we present a strategy to make blue thermally activated delayed fluorescence (TADF) polymers by directly embedding a small molecular blue TADF emitter into a poly(aryl ether) (PAE) backbone. Thanks to the oxygen-induced negligible electronic communication between neighboring TADF fragments, its corresponding blue delayed fluorescence can be inherited by the developed polymers. These polymers are free from metal catalyst contamination and show improved thermal stability. Through device optimization, a current efficiency of 29.7 cd/A (21.2 lm/W, 13.2%) is realized together with Commission Internationale de L'Eclairage coordinates of (0.18, 0.32). The value is competitive with blue phosphorescent polymers, highlighting the importance of the PAE backbone in achieving high-performance blue delayed fluorescence at a macromolecular level.