Understanding Discrete Growth in Semiconductor Nanocrystals: Nanoplatelets and Magic-Sized Clusters

ConspectusSemiconductor nanocrystals (NCs) fluoresce with a color that strongly depends on their size and shape. Thus, to obtain homogeneous optical properties, researchers have strived to synthesize particles that are uniform. However, because NCs typically grow through continuous, incremental addition of material, slight differences in the growth process between individual crystallites yield statistical distributions in size and shape, leading to inhomogeneities in their optical characteristics. Much work has focused on improving synthetic protocols to control these distributions and enhance performance. Interestingly, during these efforts, several syntheses were discovered that exhibit a different type of growth process. The NCs jump from one discrete size to the next. Through purification methods, one of these sizes can then be isolated, providing a different approach to uniform NCs. Unfortunately, the fundamental mechanism behind such discrete growth and how it differs from the conventional continuous process have remained poorly understood.Discrete growth has been observed in two major classes of NCs: semiconductor nanoplatelets (NPLs) and magic-sized clusters (MSCs). NPLs are quasi-two-dimensional crystallites that exhibit a precise thickness of only a few atomic layers but much larger lateral dimensions. During growth, NPLs slowly appear with an increasing number of monolayers. By halting this process at a specific time, NPLs with a desired thickness can then be isolated (e.g., four monolayers). Because the optical properties are primarily governed by this thickness, which is uniform, NPLs exhibit improved optical properties such as narrower fluorescence line widths.While NPLs have highly anisotropic shapes and show discrete growth only in one dimension (thickness), MSCs are isotropic particles. The name "magic" arose because a specific set of NC sizes appear during synthesis. They have been believed to represent special atomic arrangements that possess enhanced structural stability. Historically, they were very small, hence molecular-scale "clusters." Isolation of one of the MSC sizes can then, in principle, provide a uniform sample of NCs. More recently, MSC growth has been extended to larger sizes, beyond what is commonly considered to be the "cluster" regime, challenging the conventional explanation for these materials.This Account summarizes recent work by our group to understand the mechanism that governs discrete growth in semiconductor NCs. We begin by describing the synthesis of NPLs. Next, we discuss the mechanism behind the highly anisotropic shape of NPLs. We build on this by examining the ripening process in NPLs. We show that NPLs slowly appear with increasing thickness, counterintuitively through lateral growth. Then, we turn to the synthesis of MSCs, in particular focusing on their growth mechanism. Our findings indicate a strong connection between NPLs and MSCs. Finally, we review several remaining challenges for the growth of NPLs and MSCs and give a brief outlook on the future of discrete growth. By understanding the underlying process, we believe that it can be exploited more broadly, potentially moving us toward more uniform nanomaterials.