Eco-friendly, solution-processable and efficient low-energy lighting phosphors: Copper halide based hybrid semiconductors Cu4X6(L)2(X = Br, I) composed of covalent, ionic and coordinate bonds

A series of copper halide based inorganic-organic hybrid semiconductors have been synthesized. Structural analysis confirms that all compounds are composed of one-dimensional Cu4X62- anionic chains that coordinate to cationic ligands via Cu-N dative bonds. Different coordination affinities of the ligands lead to two types of ligand arrangements with various structural distortions. All compounds are highly resistant to heat and moisture as a result of the combination of coordinate and ionic bonds. Low energy emission with high efficiency is achieved for these compounds and the emission energy (∼552-615 nm) and color (yellow-orange) can be tuned by varying the ligand and halogen element. The electronic structure and luminescence mechanism are examined by both experimental and theoretical methods. More importantly, all compounds demonstrate good solubility in polar aprotic solvents, a desired property that is absent in all other CuX hybrid families of extended structures, which is attributed primarily to the ionic nature of this material class. The good solution-processability, and cost effective and easily scalable synthesis coupled with high quantum efficiencies and framework stability make these hybrid materials promising phosphors for general lighting applications