The morphology of nanocrystals serves as a powerful handle to modulate their functional properties. For semiconducting nanostructures, the shape is no less important than the size and composition, in terms of determining the electronic structure. For example, in the case of nanoplatelets (NPLs), their two-dimensional (2D) electronic structure and atomic precision along the axis of quantum confinement makes them well-suited as pure color emitters and optical gain media. In this study, we describe synthetic efforts to develop ZnSe NPLs emitting in the ultraviolet part of the spectrum. We focus on two populations of NPLs, the first having a sharp absorption onset at 345 nm and a previously unreported species with an absorption onset at 380 nm. Interestingly, we observe that the nanoplatelets are one step in a quantized reaction pathway that starts with (zero-dimensional (0D)) magic-sized clusters, then proceeds through the formation of (one-dimensional (1D)) nanowires toward the (2D) "345 nm" species of NPLs, which finally interconvert into the "380 nm" NPL species. We seek to rationalize this evolution of the morphology, in terms of a general free-energy landscape, which, under reaction control, allows for the isolation of well-defined structures, while thermodynamic control leads to the formation of three-dimensional (3D) nanocrystals.

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In contrast to molecular systems, which are defined with atomic precision, nanomaterials generally show some heterogeneity in size, shape, and composition. The sample inhomogeneity translates into a distribution of energy levels, band gaps, work functions, and other characteristics, which detrimentally affect practically every property of functional nanomaterials. We discuss a novel synthetic strategy, colloidal atomic layer deposition (c-ALD) with stationary reactant phases, which largely circumvents the limitations of traditional colloidal syntheses of nano-heterostructures with atomic precision. This approach allows for significant reduction of inhomogeneity in nanomaterials in complex nanostructures without compromising their structural perfection and enables the synthesis of epitaxial nano-heterostructures of unprecedented complexity. The improved synthetic control ultimately enables bandgap and strain engineering in colloidal nanomaterials with close to atomic accuracy. To demonstrate the power of the new c-ALD method, we synthesize a library of complex II–VI semiconductor nanoplatelet heterostructures. By combining spectroscopic and computational studies, we elucidate the subtle interplay between quantum confinement and strain effects on the optical properties of semiconductor nanostructures.

Quasi-two-dimensional nanoplatelets (NPLs) possess fundamentally different excitonic properties from zero-dimensional quantum dots. We study lateral size-dependent photon emission statistics and carrier dynamics of individual NPLs using second-order photon correlation (g(τ)) spectroscopy and photoluminescence (PL) intensity-dependent lifetime analysis. Room-temperature radiative lifetimes of NPLs can be derived from maximum PL intensity periods in PL time traces. It first decreases with NPL lateral size and then stays constant, deviating from the electric dipole approximation. Analysis of the PL time traces further reveals that the single exciton quantum yield in NPLs decreases with NPL lateral size and increases with protecting shell thickness, indicating the importance of surface passivation on NPL emission quality. Second-order photon correlation (g(τ)) studies of single NPLs show that the biexciton quantum yield is strongly dependent on the lateral size and single exciton quantum yield of the NPLs. In large NPLs with unity single exciton quantum yield, the corresponding biexciton quantum yield can reach unity. These findings reveal that by careful growth control and core-shell material engineering, NPLs can be of great potential for light amplification and integrated quantum photonic applications.

Precise patterning of quantum dot (QD) layers is an important prerequisite for fabricating QD light‐emitting diode (QLED) displays and other optoelectronic devices. However, conventional patterning methods cannot simultaneously meet the stringent requirements of resolution, throughput, and uniformity of the pattern profile while maintaining a high photoluminescence quantum yield (PLQY) of the patterned QD layers. Here, a specially designed nanocrystal ink is introduced, “photopatternable emissive nanocrystals” (PENs), which satisfies these requirements. Photoacid generators in the PEN inks allow photoresist‐free, high‐resolution optical patterning of QDs through photochemical reactions and in situ ligand exchange in QD films. Various fluorescence and electroluminescence patterns with a feature size down to ≈1.5 µm are demonstrated using red, green, and blue PEN inks. The patterned QD films maintain ≈75% of original PLQY and the electroluminescence characteristics of the patterned QLEDs are comparable to thopse of non‐patterned control devices. The patterning mechanism is elucidated by in‐depth investigation of the photochemical transformations of the photoacid generators and changes in the optical properties of the QDs at each patterning step. This advanced patterning method provides a new way for additive manufacturing of integrated optoelectronic devices using colloidal QDs.