Rational Design of Tetrahedral Derivatives as Efficient Light-Emitting Materials Based on "Super Atom" Perspective.

Traditional semiconductor quantum dots of groups II-VI are key ingredients of next-generation display technology. Yet, the majority of them contain toxic heavy-metal elements, thus calling for alternative light-emitting materials. Herein, we have explored three novel categories of multicomponent compounds, namely, tetragonal II-III2-VI4 porous ternary compounds, cubic I2-II3-VI4 ternary compounds, and cubic I-II-III3-V4 quaternary compounds. This is achieved by judicious introduction of a "super atom" perspective and concurrently varying the solid-state lattice packing of involved super atoms or the population of surrounding counter cations. Based on first-principles calculations of 392 candidate materials with designed crystal structures, 53 highly stable materials have been screened. Strikingly, 34 of them are direct-bandgap semiconductors with emitting wavelengths covering the near-infrared and visible-light regions. This work provides a comprehensive database of highly efficient light-emitting materials, which may be of interest for a broad field of optoelectronic applications.

Design Principle for Tetrahedral Semiconductors and Their Functional Derivatives: Cation Stabilizing Charged Cluster Network.

Colloidal quantum dots (QDs) of groups II-VI and III-V are key ingredients for next-generation light-emitting devices. Yet, many of them are heavy-element-containing or indirect bandgap, causing limited choice of environmental friendly efficient light-emitting materials. Herein, we resolve this issue by exploring potential derivatives of the parent semiconductors, thus expanding the material space. The key to success is the discovery of a principle for designing those materials, namely, cation stabilizing charged cluster network. Guided by this principle, three novel categories of cubic materials have been predicted, namely, porous binary compounds, I-II-VI ternary compounds, and I-II-III-V quaternary compounds. Using first-principles calculations, 65 realistic highly stable candidate materials have been theoretically screened. Their structural and compositional diversity enables a wide tunability of emitting wavelength from far-infrared to ultraviolet region. This work enriches the family of tetrahedral semiconductors and derivatives, which may be of interest for a broad field of optoelectronic applications.

Efficient Band-Edge Emission from Indirect Bandgap Semiconductor Quantum Dots upon Shell Engineering.

Environmentally friendly colloidal quantum dots (QDs) of groups III-V are in high demand for next-generation high-performance light-emitting devices for display and lighting, yet many of them (e.g., GaP) suffer from inefficient band-edge emission due to the indirect bandgap nature of their parent materials. Herein, we theoretically demonstrate that efficient band-edge emission can be activated at a critical tensile strain γc enabled by the capping shell when forming a core/shell architecture. Before γc is reached, the emission edge is dominated by dense low-intensity exciton states with a vanishing oscillator strength and a long radiative lifetime. After γc is crossed, the emission edge is dominated by high-intensity bright exciton states with a large oscillator strength and a radiative lifetime that is shorter by a few orders of magnitude. This work provides a novel strategy for realizing efficient band-edge emission of indirect semiconductor QDs via shell engineering, which is potentially implemented employing the well-established colloidal QD synthesis technique.