Wurtzite CdSe@CdS dot@platelet nanocrystals, dotshaped CdSe nanocrystals encased within epitaxially grown CdS nanoplatelets, are controllably synthesized with nearly monodisperse size and shape distribution and outstanding photoluminescence (PL) properties. The excellent size and shape control with their lateral to thickness dimension ratio up to 3:1 is achieved by systematically studying the synthetic parameters, which results in a simple, tunable, yet reproducible epitaxy scheme. These special types of core/shell nanocrystals possess two-dimensional emission dipoles with the ab plane of the wurtzite structure. While their near-unity PL quantum yield and monoexponential PL decay dynamics are at the same level of the state-of-art CdSe/CdS core/shell nanocrystals in dot shape, CdSe@CdS dot@platelet nanocrystals possess ∼2 orders of magnitude lower probability for initiating PL blinking at the single-nanocrystal level than the dot-shaped counterparts do.

This work studies extinction properties of ZnSe quantum dots terminated with either Se-surface or Zn-surface (Se-ZnSe or Zn-ZnSe QDs). In addition to commonly observed photoluminescence quenching by anionic surface sites, Se-ZnSe QDs are found to show drastic signatures of Se-surface states in their UV-visible (Vis) absorption spectra. Similar to most QDs reported in literature, monodisperse Zn-ZnSe QDs show sharp absorption features and blue-shifted yet steep absorption edge respect to the bulk bandgap. However, for monodisperse Se-ZnSe QDs, all absorption features are smeared and a low-energy tail is identified to extend to an energy window below the bulk ZnSe bandgap. Along increasing their size, a cyclic growth of ZnSe QDs switches their surface from Zn-terminated to Se-terminated ones, which confirms that the specific absorption signatures are reproducibly repeated between those of two types of the QDs. Though the extinction coefficients per unit of Se-ZnSe QDs are always larger than those of Zn-ZnSe QDs with the same size, both of them approach the same bulk limit. In addition to contribution of the lattice, extinction coefficients per nanocrystal of Zn-ZnSe QDs show an exponential term against their sizes, which is expected for quantum-confinement enhancement of electron-hole wavefunction overlapping. For Se-ZnSe QDs, there is the third term identified for their extinction coefficients per nanocrystal, which is proportional to the square of size of the QDs and consistent with surface contribution.

Synthesis of colloidal semiconductor nanocrystals with defined facet structures is challenging, though such nanocrystals are essential for fully realizing their size-dependent optical and optoelectronic properties. Here, for the mostly developed colloidal wurtzite CdSe/CdS core/shell nanocrystals, facet reconstruction is investigated under typical synthetic conditions, excluding nucleation, growth, and interparticle ripening. Within the reaction time window, two reproducible sets of facetseach with a specific group of low-index facetscan be reversibly reconstructed by switching the ligand system, indicating thermodynamic stability of each set. With a unique <0001> axis, atomic structures of the low-index facets of wurtzite nanocrystals are diverse. Experimental and theoretical studies reveal that each facet in a given set is paired with a common ligand in the solution, namely, either fatty amine and/or cadmium alkanoate. The robust bonding modes of ligands are found to be strongly facet-dependent and often unconventional, instead of following Green’s classification. Results suggest that facet-controlled nanocrystals can be synthesized by optimal facet–ligand pairing either in synthesis or after-synthesis reconstruction, implying semiconductor nanocrystal formation with size-dependent properties down to an atomic level.

Wurtzite CdSe@CdS dot@platelet nanocrystals with (001) and (00–1) polar facets as the basal planes and (100) family of nonpolar facets as the side planes are applied for studying surface defects on semiconductor nanocrystals. When they are terminated with cadmium ions coordinated with carboxylate ligands, a single set of absorption features and band-edge photoluminescence (PL) with near unity PL quantum yield and monoexponential PL decay dynamics (lifetime ∼28 ns) are observed. In addition to these spectral signatures, when the surface is converted to sulfur-terminated, a second set of sharp absorption features with decent extinction coefficients and a secondary band-edge PL with low PL quantum yield and long-lifetime (>78 ns) PL decay dynamics are reproducibly recorded. Photochemical analysis confirms that the secondary UV–vis and PL spectral features are quantitatively correlated with each other. Chemical analysis and X-ray photoelectron spectroscopy measurements confirm that such secondary spectral features are well correlated with the sulfide (such as −SH) and disulfide (such as −S–S−) surface sites of a basal plane, which likely form surface hole electronic states delocalized on the entire basal plane. Results suggest that, for studying surface defects on semiconductor nanocrystals, it is essential to prepare a nearly monodisperse surface structure in terms of facets and surface chemical bonding.

Perovskite solar cells (PSCs) are promising low-cost photovoltaic technologies with high power conversion efficiency (PCE). The crystalline quality of perovskite materials is crucial to the photovoltaic performance of the PSCs. Herein, a simple approach is introduced to prepare high-quality CHNHPbI perovskite films with larger crystalline grains and longer carriers lifetime by using magnetic field to control the nucleation and crystal growth. The fabricated planar CHNHPbI solar cells have an average PCE of 17.84% and the highest PCE of 18.56% using an optimized magnetic field at 80 mT. In contrast, the PSCs fabricated without the magnetic field give an average PCE of 15.52% and the highest PCE of 16.72%. The magnetic field action produces an ordered arrangement of the perovskite ions, improving the crystallinity of the perovskite films and resulting in a higher PCE.