Revealing Two Distinct Formation Pathways of 2D Wurtzite‐CdSe Nanocrystals Using In Situ X‐Ray Scattering

Abstract

Understanding the mechanism underlying the formation of quantum‐sized semiconductor nanocrystals is crucial for controlling their synthesis for a wide array of applications. However, most studies of 2D CdSe nanocrystals have relied predominantly on ex situ analyses, obscuring key intermediate stages and raising fundamental questions regarding their lateral shapes. Herein, the formation pathways of two distinct quantum‐sized 2D wurtzite‐CdSe nanocrystals — nanoribbons and nanosheets — by employing a comprehensive approach, combining in situ small‐angle X‐ray scattering techniques with various ex situ characterization methods is studied. Although both nanostructures share the same thickness of ≈1.4 nm, they display contrasting lateral dimensions. The findings reveal the pivotal role of Se precursor reactivity in determining two distinct synthesis pathways. Specifically, highly reactive precursors promote the formation of the nanocluster‐lamellar assemblies, leading to the synthesis of 2D nanoribbons with elongated shapes. In contrast, mild precursors produce nanosheets from a tiny seed of 2D nuclei, and the lateral growth is regulated by chloride ions, rather than relying on nanocluster‐lamellar assemblies or Cd(halide)2–alkylamine templates, resulting in 2D nanocrystals with relatively shorter lengths. These findings significantly advance the understanding of the growth mechanism governing quantum‐sized 2D semiconductor nanocrystals and offer valuable guidelines for their rational synthesis.

Recent advances in photoelectrochemical hydrogen production using I–III–VI quantum dots

“…Colloidal semiconductor quantum dots (QDs), tiny nanoparticles with dimensions spanning just a few nanometers, 26–31 exhibit unique size- and shape-dependent properties compared to their bulk counterparts resulting from quantum confinement effects. 32–35 They have emerged as efficient and versatile sensitizers for the photoelectrodes (usually, photoanodes) of PEC devices due to several advantages: tunable bandgap, large light absorption coefficient, facile synthesis, ease of surface functionalization, and solution processability. 15–19,36–38 The discussed drawbacks ( i.e.…”