Structure-Property Correlation in Luminescent Indolo[3,2-b]indole (IDID) Derivatives: Unraveling the Mechanism of High Efficiency Thermally Activated Delayed Fluorescence (TADF).

A series of indolo[3,2-b]indole (IDID) derivatives are designed as a novel structural platform for thermally activated delayed fluorescence (TADF) emitters. Intramolecular charge transfer (ICT)-type molecules consisting of IDID donor (D) and various acceptor (A) moieties are synthesized and characterized in the protocol of the systematical structure-property correlation. IDID derivatives exhibit high efficiency, prompt fluorescence as well as TADF with emission ranges tuned by the chemical structure of the acceptor units. Interestingly, almost all of the IDID derivatives show an identical energy level of the lowest triplet excited state (T1) attributed to the locally excited triplet state of the IDID backbone (3LEID), while that of their lowest singlet excited state (S1) is largely tuned by varying the acceptor units. Thus, we demonstrate the underlying mechanism in terms of the molecular engineering. Among the compounds, Tria-phIDID and BP-phIDID generate efficient delayed fluorescence based on the small energy gap between the lowest singlet and triplet excited states (ΔEST) and mediation of the 3LEID state. Organic light-emitting diodes with these Tria-phIDID and BP-phIDID as a dopant in the emitting layer show highly efficient electroluminescence with maximum external quantum efficiencies of 20.8% and 13.9%, respectively.

Highly Luminescent 2D-Type Slab Crystals Based on a Molecular Charge-Transfer Complex as Promising Organic Light-Emitting Transistor Materials.

A new 2:1 donor (D):acceptor (A) mixed-stacked charge-transfer (CT) cocrystal comprising isometrically structured dicyanodistyrylbenzene-based D and A molecules is designed and synthesized. Uniform 2D-type morphology is manifested by the exquisite interplay of intermolecular interactions. In addition to its appealing structural features, unique optoelectronic properties are unveiled. Exceptionally high photoluminescence quantum yield (ΦF ≈ 60%) is realized by non-negligible oscillator strength of the S1 transition, and rigidified 2D-type structure. Moreover, this luminescent 2D-type CT crystal exhibits balanced ambipolar transport (µh and µe of ≈10-4 cm2 V-1 s-1 ). As a consequence of such unique optoelectronic characteristics, the first CT electroluminescence is demonstrated in a single active-layered organic light-emitting transistor (OLET) device. The external quantum efficiency of this OLET is as high as 1.5% to suggest a promising potential of luminescent mixed-stacked CT cocrystals in OLET applications.

Indolo[3,2-b]indole-based crystalline hole-transporting material for highly efficient perovskite solar cells.

We have designed and synthesized fluorinated indolo[3,2-b]indole (IDID) derivatives as crystalline hole-transporting materials (HTM) for perovskite solar cells. The fluorinated IDID backbone enables a tight molecular arrangement stacked by strong π-π interactions, leading to a higher hole mobility than that of the current HTM standard, p,p-spiro-OMeTAD, with a spherical shape and amorphous morphology. Moreover, the photoluminescence quenching in a perovskite/HTM film is more effective at the interface of the perovskite with IDIDF as compared to that of p,p-spiro-OMeTAD. As a consequence, the device fabricated using IDIDF shows superior photovoltaic properties compared to that using p,p-spiro-OMeTAD, exhibiting an optimal performance of 19%. Thus, this remarkable result demonstrates IDID core-based materials as a new class of HTMs for highly efficient perovskite solar cells.

Patterned Taping: A High-Efficiency Soft Lithographic Method for Universal Thin Film Patterning.

As a universal lithographic technique for microscale/nanoscale film patterns, we develop a strategy for the use of soft lithographically patterned pressure-sensitive tape (patterned tape) as a pattern-transporting stamp material. Patterning was successfully implemented through the selective detachment and/or attachment of various thin films, including organic and metallic layers demanding no subsequent physical, thermal, or chemical treatment, as this incurs the risk of the deformation of the thin film and the deterioration of its functionalities. Its features of universal adhesion and flexibility enable pressure-sensitive tapes to form patterns on a variety of surfaces: organic, polymeric, and inorganic surfaces as well as flat, curved, uneven, and flexible substrates. Moreover, the proposed technique boasts the unique and distinct advantages of short operation time, supreme patterning yield, and multilayer stacking capability, which suggest considerable potential for their application to advanced optoelectronic device fabrication.

Stimuli-Responsive Reversible Fluorescence Switching in a Crystalline Donor-Acceptor Mixture Film: Mixed Stack Charge-Transfer Emission versus Segregated Stack Monomer Emission.

We report on a molecularly tailored 1:1 donor-acceptor (D-A) charge-transfer (CT) cocrystal that manifests strongly red-shifted CT luminescence characteristics, as well as noteworthy reconfigurable self-assembling behaviors. A loosely packed molecular organization is obtained as a consequence of the noncentrosymmetric chemical structure of molecule A1, which gives rise to considerable free volume and weak intermolecular interactions. The stacking features of the CT complex result in an external stimuli-responsive molecular stacking reorganization between the mixed and demixed phases of the D-A pair. Accordingly, high-contrast fluorescence switching (red↔blue) is realized on the basis of the strong alternation of the electronic properties between the mixed and demixed phases. A combination of structural, spectroscopic, and computational studies reveal the underlying mechanism of this stimuli-responsive behavior.