Despite recent achievements to reduce surface quenching in NaYF₄:Yb,Er nanocrystals, a complete understanding of how the nanocrystal size affects the brightness of upconversion luminescence is still incomplete. Here we investigated upconversion luminescence of Yb,Er-doped nanocrystals in a broad range of sizes from 6 nm to 45 nm (cubic or hexagonal phases), displaying an increasing red-to-green luminescence intensity ratio and reduced luminescence lifetimes with decreasing size. By analyzing the upconversion process with a set of rate equations, we found that their asymptotic analytic solutions explain lower decay rates of red compared to green upconversion luminescence. Furthermore, we quantified the effect of the surface on luminescence lifetime in a model where nanocrystal emitters are divided between the near-surface and inside regions of each nanocrystal. We clarify the influence of the four nonradiative recombination mechanisms (intrinsic phonon modes, vibration energy of surface ligands, solvent-mediated quenching, and surface defects) on the decay rates for different-size nanocrystals, and find that the defect density dominates decay rates for small (below 15 nm) nanocrystals. Our results indicate that a defect-reduction strategy is a key step in producing small upconversion nanocrystals with increased brightness for a variety of bioimaging and biosensing applications.

The ultimate frontier in nanomaterials engineering is to realize their composition control with atomic scale precision to enable fabrication of nanoparticles with desirable size, shape and surface properties. Such control becomes even more useful when growing hybrid nanocrystals designed to integrate multiple functionalities. Here we report achieving such degree of control in a family of rare-earth-doped nanomaterials. We experimentally verify the co-existence and different roles of oleate anions (OA⁻) and molecules (OAH) in the crystal formation. We identify that the control over the ratio of OA⁻ to OAH can be used to directionally inhibit, promote or etch the crystallographic facets of the nanoparticles. This control enables selective grafting of shells with complex morphologies grown over nanocrystal cores, thus allowing the fabrication of a diverse library of monodisperse sub-50 nm nanoparticles. With such programmable additive and subtractive engineering a variety of three-dimensional shapes can be implemented using a bottom–up scalable approach.