Self-assembled colloidal crystals (CCs) or nanoparticle (NPs) superlattices have attracted significant attention due to their potential applications in many fields. However, due to the complex interactions that govern the self-assembly, it is difficult to predict and control the superstructure organization of CCs. Herein, a facile yet effective way is demonstrated to fabricate oriented CCs from capillary assembly of polymer-tethered gold NPs (AuNPs). Assembly mechanism of polymer-tethered AuNPs and their superlattice structures are systematically studied by in situ small-angle X-ray scattering (SAXS) technology. The results show that the oriented CCs of polymer-tethered AuNPs can be obtained upon solvent evaporation in a capillary tube and the oriented structure is mainly determined by the chain length of polymer ligands and size of AuNPs. Assembly of AuNPs tethered by short-chain ligand can result in oriented face-centered cubic (fcc) superlattice, whereas AuNPs tethered by long-chain ligand can assemble into an oriented body-centered tetragonal (bct) superlattice structure. Interestingly, in situ SAXS study shows that for the sample of bct superlattice structure, a transformation from fcc to bct superlattice upon solvent evaporation is observed, which strongly depends on chain length of ligands. This work provides a useful guide for polymer-tethered AuNPs to prepare orientation colloidal crystals.
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