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High-resolution transmission electron microscopy results reveal that oriented-attachment- and defect-dependent mechanisms rule the size and shape evolution of the monodispersed PbTe quantum dots (QDs). The former is characterized by the growth of quasi-cubic PbTe QDs, which depends on both the geometric constraints imposed by the 200 facets and the defect-free lattice, while the latter one is a defect-dependent mechanism which gives way to the formation of decahedral PbTe QDs (∼6 nm). Experimentally, formaldehyde is an important paramet