Spiro-Based Thermally Activated Delayed Fluorescence Emitters with Reduced Nonradiative Decay for High-Quantum-Efficiency, Low-Roll-Off, Organic Light-Emitting Diodes

Herein, we report the use of spiro-configured fluorene-xanthene scaffolds as a novel, promising, and effective strategy in thermally activated delayed fluorescence (TADF) emitter design to attain high photoluminescence quantum yields (Φ_PL), short delayed luminescence lifetime, high external quantum efficiency (EQE), and minimum efficiency roll-off characteristics in organic light-emitting diodes (OLEDs). The optoelectronic and electroluminescence properties of SFX (spiro-(fluorene-9,9′-xanthene))-based emitters (SFX-PO-DPA, SFX-PO-DPA-Me, and SFX-PO-DPA-OMe) were investigated both theoretically and experimentally. All three emitters exhibited sky blue to green emission enabled by a Herzberg–Teller mechanism in the excited state. They possess short excited-state delayed lifetimes (<10 μs), high photoluminescence quantum yields (Φ_PL ∼ 70%), and small singlet–triplet splitting energies (ΔE_ST < 0.10 eV) in the doped films in an mCP host matrix. The OLEDs showed some of the highest EQEs using spiro-containing emitters where maximum external quantum efficiencies (EQE_max) of 11 and 16% were obtained for devices using SFX-PO-DPA and SFX-PO-DPA-OMe, respectively. Further, a record EQE_max of 23% for a spiro-based emitter coupled with a low efficiency roll-off (19% at 100 cd m^–2) was attained with SFX-PO-DPA-Me.