Gold Nanorods Dispersed in Homopolymer Films: Optical Properties Controlled by Self-Assembly and Percolation of Nanorods

In this paper, polymer nanocomposite films containing gold nanorods (AuNRs) and poly(2-vinyl pyridine) (P2VP) have been investigated for their structure-optical property relationship. Using transmission electron microscopy (TEM), the assembly of AuNRs (7.9 nm × 28.4 nm) grafted with a P2VP brush in P2VP films is examined as a function of the AuNR volume fraction Ø(AuNRs) and film thickness h. For h ∼ 40 nm, AuNRs are confined to align parallel to the film and uniformly dispersed at low Ø(AuNRs). Upon increasing Ø(AuNRs), nanorods form discrete aggregates containing mainly side-by-side arrays due to depletion-attraction forces. For Ø(AuNRs) = 2.7%, AuNRs assemble into a 2D network where the discrete aggregates are connected by end-to-end linked nanorods. As Ø(AuNRs) further increases, the polymer-rich regions of the network fill in with nanorods and rod overlap is observed. Monte Carlo simulations capture the experimentally observed morphologies. The effect of film thickness is investigated at Ø(AuNRs) = 2.7%, where thicker films (40 and 70 nm) show a dense array of percolated nanorods and thinner films (20 nm) exhibit mainly isolated nanorods. Using Rutherford backscattering spectrometry (RBS), the AuNRs are observed to segregate near the substrate during spin-casting. Optically, the longitudinal surface plasmon resonance (LSPR) peaks are correlated with the local orientation of the AuNRs, where side-by-side and end-to-end alignments induce blue and red shifts, respectively. The LSPR undergoes a red shift up to 51 nm as Ø(AuNRs) increases from 1.6 to 2.7%. These studies indicate that the optical properties of polymer nanocomposite films containing gold nanorods can be fine-tuned by changing Ø(AuNRs) and h. These results are broadly applicable and provide guidelines for dispersing other functional nanoparticles, such as quantum dots and carbon nanotubes.