Using in situ high-resolution TEM, we study the structure and dynamics of well-defined edge dislocations in imperfectly attached PbTe nanocrystals. We identify that attachment of PbTe nanocrystals on both {100} and {110} facets gives rise to b = a/2⟨110⟩ edge dislocations. Based on the Burgers vector of individual dislocations, we can identify the glide plane of the dislocations. We observe that defects in particles attached on {100} facets have glide planes that quickly intersect the surface, and HRTEM movies show that the defects follow the glide plane to the surface. For {110} attached particles, the glide plane is collinear with the attachment direction, which does not provide an easy path for the dislocation to reach the surface. Indeed, HRTEM movies of dislocations for {110} attached particles show that defect removal is much slower. Further, we observe conversion from pure edge dislocations in imperfectly attached particles to dislocations with mixed edge and screw character, which has important implications for crystal growth. Finally, we observe that dislocations initially closer to the surface have a higher speed of removal, consistent with the strong dislocation free surface attractive force. Our results provide important design rules for defect-free attachment of preformed nanocrystals into epitaxial assemblies.

Graphene liquid cell electron microscopy has the necessary temporal and spatial resolution to enable the in situ observation of nanoscale dynamics in solution. However, the chemistry of the solution in the liquid cell during imaging is as yet poorly understood due to the generation of a complex mixture of radiolysis products by the electron beam. In this work, the etching trajectories of nanocrystals were used as a probe to determine the effect of the electron beam dose rate and preloaded etchant, FeCl 3 , on the chemistry of the liquid cell. Initially, illuminating the sample at a low electron beam dose rate generates hydrogen bubbles, providing a reservoir of sacrificial reductant. Increasing the electron beam dose rate leads to a constant etching rate that varies linearly with the electron beam dose rate. Comparing these results with the oxidation potentials of the species in solution, the electron beam likely controls the total concentration of oxidative species in solution and FeCl 3 likely controls the relative ratio of oxidative species, independently determining the etching rate and chemical potential of the reaction, respectively. Correlating these liquid cell etching results with the ex situ oxidative etching of gold nanocrystals using FeCl 3 provides further insight into the liquid cell chemistry while corroborating the liquid cell dynamics with ex situ synthetic behavior. This understanding of the chemistry in the liquid cell will allow researchers to better control the liquid cell electron microscopy environment, allowing new nanoscale materials science experiments to be conducted systematically in a reproducible manner.

The goal of this work is to identify favored pathways for preparation of defect resilient attached wurtzite CdX (X = S, Se, Te) nanocrystals. We seek guidelines for oriented attachment of faceted nanocrystals that are most likely to yield pairs of nanocrystals with either few or no electronic defects, or electronic defects that are in and of themselves desirable and stable. Using a combination of in-situ high resolution transmission electron microscopy (HRTEM) and electronic structure calculations, we evaluate the relative merits of atomic attachment of wurtzite CdSe nanocrystals on the {11 � 00} or {112 � 0} family of facets. Pairwise attachment on either facet can lead to perfect interfaces, provided the nanocrystal facets are perfectly flat and the angles between the nanocrystals can adjust during the assembly. Considering defective attachment, we observe for {11 � 00} facet attachment that only one type of edge dislocation forms, creating deep hole traps. For {112 � 0} facet attachment, we observe that four distinct types of dislocations form, some of which lead to deep hole traps while others only to shallow hole traps. HRTEM movies of the dislocation dynamics show that dislocations at {11 � 00} interfaces can be removed, albeit slowly. Whereas only some extended dislocations at {112 � 0} interfaces could be removed, others were trapped at the interface. Based on these insights, we identify the most resilient pathways to atomic attachment of pairs of wurtzite CdX nanocrystals and consider how these insights can translate to creation of electronically useful materials from quantum dots with other crystal structures.