Achieving efficient solution-processed ultra-deep-blue OLEDs remains a challenge. Herein, a methyl-modification strategy is proposed to overcome weak intramolecular charge transfer and large energy gap between the singlet and triplet states (ΔEST) of ultra-deep-blue through-space charge transfer (TSCT)- thermally activated delayed fluorescence (TADF) emitters. In this way, the reverse intersystem crossing (RISC) processes are found to be effective from T1 to S1 and can be accelerated with the assistance of T2. As a result, the ultra-deep-blue TSCT emitter 3MeCz-BO exhibits a minimized ΔEST of 0.02 eV, and an enhanced RISC rate of 3.71 × 105 s-1. Additionally, this modification can improve the solubility to enable the fabrication of solution-processed organic light-emitting diodes (OLEDs). The maximum external quantum efficiency of the 3MeCz-BO-based solution-processed OLED achieves 10.06%, with a Commission Internationale de L’Eclairage (CIE) coordinate of (0.151, 0.051) and a luminance of 1334 cd m–2. This work is the first case of developing high-performance ultra-deep-blue solution-processed TSCT-TADF OLEDs, which show comparable performance to vacuum-deposited OLEDs. Furthermore, 3MeCz-BO-based OLED fits well within the standard Red Green Blue (sRGB) of CIE (0.15, 0.06), and is close to the CIE (0.131, 0.046) for the Rec. 2020 standard, implying its potential application in colorful display devices.
