Copper(I) iodide (CuI)-based inorganic-organic hybrid materials in the general chemical formula of CuI(L) are well-known for their structural diversity and strong photoluminescence and are therefore considered promising candidates for a number of optical applications. In this work, we demonstrate a systematic, bottom-up precursor approach to developing a series of CuI(L) network structures built on CuI rhomboid dimers. These compounds combine strong luminescence due to the CuI inorganic modules and significantly enhanced thermal stability as a result of connecting individual building units into robust, extended networks. Examination of their optical properties reveals that these materials not only exhibit exceptionally high photoluminescence performance (with internal quantum yield up to 95%) but also that their emission energy and color are systematically tunable through modification of the organic component. Results from density functional theory calculations provide convincing correlations between these materials' crystal structures and chemical compositions and their optophysical properties. The advantages of cost-effective, solution-processable, easily scalable and fully controllable synthesis as well as high quantum efficiency with improved thermal stability, make this phosphor family a promising candidate for alternative, RE-free phosphors in general lighting and illumination. This solution-based precursor approach creates a new blueprint for the rational design and controlled synthesis of inorganic-organic hybrid materials.
As one of the most rapidly evolving branches of solid-state lighting technologies, light emitting diodes (LEDs) are gradually replacing conventional lighting sources due to their advantages in energy saving and environmental protection. At the present time, commercially available white light emitting diodes (WLEDs) are predominantly phosphor based (e.g., a yellow-emitting phosphor, such as cerium-doped yttrium aluminum garnet or (YAG):Ce(3+), coupled with a blue-emitting InGaN/GaN diode), which rely heavily on rare-earth (RE) metals. To avoid potential supply risks of these elements, we have developed an inorganic-organic hybrid phosphor family based on I-VII binary semiconductors. The hybrid phosphor materials are totally free of rare-earth metals. They can be synthesized by a simple, low-cost solution process and are easily scalable. Their band gap and emission energy, intensity, and color can be systematically tuned by incorporating ligands with suitable electronic properties. High quantum efficiency is achieved for some of these compounds. Such features make this group of materials promising candidates as alternative phosphors for use in general lighting devices.
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