Nanoparticle Assemblies in Thin Films of Supramolecular Nanocomposites

Abstract

We demonstrated a versatile approach to obtain layered nanoparticle sheets with in-plane hexagonal order and 3-D ordered arrays of single nanoparticle chains in thin films upon blending nanoparticles with block copolymer (BCP)-based supramolecules. Basic understanding on the thermodynamic and kinetic aspects of the assembly process paved a path to manipulate these assemblies to meet demands in nanoparticle-based device fabrication and understand structure-property correlations.

Rapid fabrication of hierarchically structured supramolecular nanocomposite thin films in one minute

“…In thin film, after solvent annealing using chloroform, it forms hexagonally packed 3D nanoparticle arrays where the Au nanoparticles are selectively located at the interstitial sites in the P4VP(PDP) matrix (Fig. 1) 29 .…”

“…The presence of small molecules eliminates the need to modify either the nanoparticle ligand or polymer for nanoparticle incorporation and improve inter-particle ordering within BCP microdomains. One-, two-and three-dimensional (3D) nanoparticle arrays can be obtained in thin films of supramolecular nanocomposites via solvent annealing for a range of nanoparticles or nanoparticle mixtures 17,19,20,28,29 . Kinetically, the presence of small molecules also provides unique opportunities to manipulate the energy landscape of the assembly process and to accelerate the assembly kinetics so that inherent properties of nanoparticles can be maintained and continuous thin film processing techniques can be implemented for device fabrication.…”

Block copolymer–nanoparticle composites: Structure, functional properties, and processing

“…Certain additives can interact selectively with one of the blocks of a BCP and change its conformation from flexible to rigid [74,[104][105][106][107][108]. For example, 3-n-pentadecyl phenol (PDP) (with PDP/4VP mole ratio in the range 1-3) changed the conformation of poly(4-vinyl pyridine) (P4VP) from coil (flexible) to rigid as PDP hydrogen bonded with P4VP [74].…”

End-to-End Alignment of Nanorods in Thin Films

“…The use of P4VP(PDP) 1.7 comb blocks rather than a typical coil polymer block increases the energy required for the deformation of the polymer chain and improves the geometric confinement of the nanorods within the matrix composed of the comb block. Figure 1a schematically shows one hypothetical coassembly, where NRs localize in the same location as the spherical particles 41 and form end-toend arrays.…”