II–VI Organic–Inorganic Hybrid Nanostructures with Greatly Enhanced Optoelectronic Properties, Perfectly Ordered Structures, and Shelf Stability of Over 15 Years

Organic–inorganic hybrids may offer material properties not available from their inorganic components. However, they are typically less stable and disordered. Long-term stability study of the hybrid materials, over the anticipated lifespan of a real-world electronic device, is practically nonexistent. Disordering, prevalent in most nanostructure assemblies, is a prominent adversary to quantum coherence. A family of perfectly ordered II–VI-based hybrid nanostructures has been shown to possess many unusual properties and potential applications. Here, using a prototype structure β-ZnTe­(en)_0.5a hybrid superlatticeand applying an array of optical, structural, surface, thermal, and electrical characterization techniques, in conjunction with density-functional theory calculations, we have performed a comprehensive and correlative study of the crystalline quality, structural degradation, electronic, optical, and transport properties on samples from over 15 years old to the recently synthesized. The findings show that not only do they exhibit an exceptionally high level of crystallinity in both macroscopic and microscopic scale, comparable to high-quality binary semiconductors; and greatly enhanced material properties, compared to those of the inorganic constituents; but also, some of them over 15 years old remain as good in structure and property as freshly made ones. This study reveals (1) what level of structural perfectness is achievable in a complex organic–inorganic hybrid structure or a man-made superlattice, suggesting a nontraditional strategy to make periodically stacked heterostructures with abrupt interfaces; and (2) how the stability of a hybrid material is affected differently by its intrinsic attributes, primarily formation energy, and extrinsic factors, such as surface and defects. By correlating the rarely found long-term stability with the calculated relatively large formation energy of β-ZnTe­(en)_0.5 and contrasting with the case of hybrid perovskite, this work illustrates that formation energy can serve as an effective screening parameter for the long-term stability potential of hybrid materials. The results of the prototype II–VI hybrid structures will, on one hand, inspire directions for future exploration of the hybrid materials, and, on the other hand, provide metrics for assessing the structural perfectness and long-term stability of the hybrid materials.