Ligand-mediate exciton allocation enables efficient cluster-based white light-emitting diodes via single and heavy doping.

Despite potential in high-resolution and low-cost displays and lighting, multi-doping structures and low concentrations (<1%) limit repeatability and stability of single-emissive-layer white light-emitting devices. Herein, we report a singly doped white-emitting system of blue thermally activated delayed fluorescence host matrix (CzAcSF) doped by yellow CuI cluster ([tBCzDppy]CuI). CzAcSF:x% [tBCzDppy]CuI films realize photo- and electro-luminescence colors from cool white to warm white at x = 20-40. The external quantum efficiency of 23.5% was achieved at x = 30, indicating the record-high efficiency among solution-processed analogs and the largest doping concentration among efficient white light-emitting devices. It shows that di(tert-butyl)carbazole moieties in [tBCzDppy]CuI provide high-lying excited energy levels at~2.6 eV to mediate energy transfer from CzAcSF (2.9 eV) to coordinated CuI (2.2 eV). Our results demonstrate the antenna effect of ligands on optimizing charge and energy transfer in organic-cluster systems and superiority of white cluster light-emitting diodes in practical applications.