The equilibrium phase of cesium lead iodide (CsPbI3) at room temperature is yellow and optically inactive due to its indirect band gap. The metastable black phase of CsPbI3 on the other hand exhibits optical properties that are suitable for photovoltaic and light-emitting devices. Here, we examine the stability of the black phase of ligand-stabilized CsPbI3 nanocrystals heated in humid air. Water vapor is known to catalyze the transition of CsPbI3 from the black phase to the yellow phase. Uniform nanocrystals with cube shape were synthesized with capping ligand mixtures of oleylamine and oleic acid or diisooctylphosphinic acid, assembled into superlattices with preferred crystal orientation, and studied using grazing incidence small- and wide-angle X-ray scattering with in situ heating. The black-phase nanocrystals are found to inhabit the γ-orthorhombic phase and do not revert to the equilibrium yellow δ-orthorhombic phase until reaching a relatively high temperature, between 170 and 200 °C, coinciding with superlattice degradation.

Grazing incidence small angle X-ray scattering (GISAXS) measurements reveal that superlattices of 1.7 nm diameter, gold (Au) nanocrystals capped with octadecanethiol become significantly more ordered when heated to moderate temperatures (50-60 °C). This enhancement in order is reversible and the superlattice returns to its initially disordered structure when cooled back to room temperature. Disorder-order transition temperatures were estimated from the GISAXS data using the Hansen-Verlet criterion. Differential scanning calorimetry (DSC) measurements of the superlattices exhibited exotherms (associated with disordering during cooling) and endotherms (associated with ordering during heating) near the transition temperatures. The superlattice transition temperatures also correspond approximately to the melting and solidification points of octadecanethiol. Therefore, it appears that a change in capping ligand packing that occurs upon ligand melting underlies the structural transition of the superlattices. We liken the heat-induced ordering of the superlattices to an inverse melting transition.

Uniform silicon nanocrystals were synthesized with cuboctahedral shape and passivated with 1-dodecene capping ligands. Transmission electron microscopy, electron diffraction, and grazing incidence wide-angle and small-angle X-ray scattering show that these soft cuboctahedra assemble into face-centered cubic superlattices with orientational order. The preferred nanocrystal orientation was found to depend on the orientation of the superlattices on the substrate, indicating that the interactions with the substrate and assembly kinetics can influence the orientation of faceted nanocrystals in superlattices.

Colloidal nanocrystals of CH 3 NH 3 PbI 3 (MAPI) with the tetragonal crystal structure and cuboidal shape terminated by {110} and {002} facets were assembled into superlattices with cubatic structure and heated under nitrogen while collecting in situ grazing incidence small-and wide-angle Xray scattering (GISAXS and GIWAXS). The nanocrystals have completed a tetragonal-to-cubic phase transition by 60 °C similar to bulk films. GISAXS shows that the superlattice remains stable until 90 °C. At this temperature, GIWAXS reveals the evolution of PbI 2 . In situ photoluminescence shows that PbI 2 begins to form at 75 °C, which is about 10−25 °C lower than in bulk MAPI films. Another difference compared to bulk MAPI is that both hexagonal and rhombohedral phases of PbI 2 are observed as thermal degradation products, when the nanocrystals are heated up to 150 °C. 3 3 3 3 2 2(2)

We recently observed that a disordered assembly of octadecanethiol-capped gold (Au) nanocrystals can order when heated from room temperature to 60 °C [Yu, Y.; Jain, A.; Guillaussier, A.; Voggu, V. R.; Truskett, T. M.; Smilgies, D.-M.; Korgel, B. A. Faraday Discuss. 2015, 181, 181–192]. This “inverse melting” structural transition was reversible and occurred near the melting-solidification temperature of the capping ligands. To determine the generality of this phenomenon, we studied by in situ grazing incidence small-angle X-ray scattering (GISAXS) the structure of assemblies of Au nanocrystals with shorter C12 and C5 alkanethiol capping ligands that form ordered superlattices at room temperature and have a ligand melting-solidification temperature below room temperature. Superlattices of dodecanethiol-capped Au nanocrystals disorder when cooled below 260 K, which is the melting-solidification temperature for dodecanethiol. Au nanocrystals capped with even shorter pentanethiol ligands that have a melting transition below 100 K (the lowest experimentally accessible temperature) do not undergo the disorder transition.