Orientationally ordered silicon nanocrystal cuboctahedra in superlattices

This is an open access article published under an ACS AuthorChoice License. See Standard ACS AuthorChoice/Editors' Choice Usage Agreement - https://pubs.acs.org/page/policy/authorchoice_termsofuse.htmlUniform 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

Directing and characterizing silicon nanocrystal self-assembly

Silicon nanocrystals or quantum dots are non-toxic and exhibit unique size tunable opto-electronic properties. Their bright photoluminescence as well as their ability to generate more than one electron per photon absorbed make them good candidates for both bioimaging and photovoltaics applications. Their surface can be functionalized with different ligands that protect them against oxidation and allow them to be dispersed and stable in a variety of solvents. Dodecane capped silicon nanocrystals can be dispersed in non-polar solvents such as hexane, chloroform or toluene for years without aggregating nor losing their optical properties. When deposited on a substrate under certain conditions, dodecane capped silicon nanocrystals can self-assemble into 2D or 3D periodic arrays of quantum dots called superlattices. These ordered structures of nanocrystals can potentially enhance the conductivity of the nanocrystal thin film which would be helpful for photovoltaic applications. In order to perform charge transport measurements through superlattices, large uniform ordered nanocrystal films must be achieved. Two deposition processes are studied and optimized to lead to the formation of several microns large both 2D and 3D silicon nanocrystals superlattices. A model is developed to understand the superlattice growth mechanism and several parameters are found to influence the superlattice morphology. Silicon nanocrystals can also be functionalized with chromophores to enhance their optical absorption. This can improve efficiencies of self-assembled quantum dots solar devices. Silicon nanocrystals functionalized with pyrene units are studied using transient absorption spectroscopy. They exhibit enhanced optical absorption and efficient carrier multiplication via energy transfer from the pyrene unit to the nanocrystal core. Finally, carboxylate terminated silicon nanocrystals are stable in water over a wide range of pH which makes them suitable for self-assembly in aqueous media. Incorporating biological receptor-substrate sites to the nanocrystal surface can permit recognition-driven self-assembly. Carbodiimide activation is commonly used to biofunctionalize nanoparticles. This chemistry is tested to attach an amine terminated PEG (polyethylene glycol) molecule to silicon nanocrystals. PEG functionalization is found to improve silicon nanocrystal photoluminescence stability.Chemical Engineerin

Bubble Assemblies of Nanocrystals: Superlattices without a Substrate

A method was developed to create free-standing nanocrystal films in the form of solidified bubbles. Bubbles of octadecanethiol-capped gold nanocrystals were studied by in situ grazing incidence small-angle X-ray scattering (GISAXS) to determine how the absence of an underlying substrate influences a disorder–order transition of a nanocrystal superlattice. We find that the presence of the substrate does not significantly change the nature of the disorder–order transition but does lead to reduced interparticle separation and reduced thermal expansion. Bubble assemblies of silicon and copper selenide nanocrystals are also demonstrated

Structure–Properties Correlation in Si Nanoparticles by Total Scattering and Computer Simulations

High-energy synchrotron X-ray diffraction coupled to atomic pair distribution function analysis and computer simulations is used to determine the atomic-scale structure of silicon (Si) nanoparticles obtained by two different synthetic routes. Results show that Si nanoparticles may have significant structural differences depending on the synthesis route and surface chemistry. In this case, one method produced Si nanoparticles that are highly crystalline but surface oxidized, whereas a different method yields organic ligand-passivated nanoparticles without surface oxide but that are structurally distorted at the atomic scale. Particular structural features of the oxide-free Si nanoparticles such as average first coordination numbers, length of structural coherence, and degree of local distortions are compared to their optical properties such as photoluminescence emission energy, quantum yield, and Raman spectra. A clear structure–properties correlation is observed indicating that the former may need to be taken into account when considering the latter

Orientationally ordered silicon nanocrystal cuboctahedra in superlattices

This is an open access article published under an ACS AuthorChoice License. See Standard ACS AuthorChoice/Editors' Choice Usage Agreement - https://pubs.acs.org/page/policy/authorchoice_termsofuse.htmlUniform 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

Cooling Dodecanethiol-Capped 2 nm Diameter Gold Nanocrystal Superlattices below Room Temperature Induces a Reversible Order–Disorder Structure Transition

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. <i>Faraday Discuss.</i> <b>2015</b>, <i>181</i>, 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

Silicon Nanocrystal Superlattice Nucleation and Growth

Colloidal dodecene-passivated silicon (Si) nanocrystals were dispersed in hexane or chloroform and deposited onto substrates as face-centered cubic superlattices by slowly evaporating the solvent. The uniformity of the nanocrystals enables extended order; however, the solvent and the evaporation protocol significantly influence the self-assembly process, determining the morphology of the films, the extent of order, and the superlattice orientation on the substrate. Chloroform yielded superlattices with step-flow growth morphologies and (111)_SL, (100)_SL, and (110)_SL orientations. Hexane led to mostly island morphologies when evaporated at room temperature with exclusively (111)_SL orientations. Higher evaporation temperatures led to more extensive step-flow deposition. A model for the surface diffusion of nanocrystals adsorbed on the superlattice surface is developed

Orientationally Ordered Silicon Nanocrystal Cuboctahedra in Superlattices

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