Nanorod position and orientation in vertical cylinder block copolymer films.

The self-assembly of gold nanorods (AuNRs) of different sizes with a block copolymer (BCP) is studied. Polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) films containing P2VP functionalized AuNRs are solvent annealed resulting in a BCP morphology of vertical P2VP cylinders in a PS matrix. At the surface of the PS-b-P2VP films long AuNRs are found in the bridging and vertical states. The bridging state is where the long axis of the AuNR is parallel to the film surface, the AuNR is embedded in the film, and each end of the AuNR is at the top of nearest neighbor P2VP cylinders. The vertical state is where the AuNR is localized within a vertical P2VP cylinder, the AuNR long axis is perpendicular to the film surface and the upper tip of the AuNR is at the film surface. Short AuNRs were found in the bridging and vertical states as well as in a state not observed for the long AuNRs, the centered state. The centered state is where an AuNR has its long axis parallel to the film surface, is embedded in the film, and is centered over a vertical P2VP cylinder. Hybrid particle-field theory (HPFT) simulations modeling the experimental system predict that for the long AuNRs only the bridging state should be observed while for the short AuNRs only the bridging and centered states should be observed. Possible explanations for why the vertical state is observed in experiments despite being thermodynamically unfavorable in simulations are discussed. HPFT simulations also show that when a nanorod is in the bridging state the two cylinders it bridges remain intact and extend from the nanorod to the substrate. Further, the minority block of the BCP is shown to wet the bottom of the bridging nanorod. The bridging state is very promising for the future development of self-assembled nanoscale devices.

Equilibrium Field Theoretic Study of Nanoparticle Interactions in Diblock Copolymer Melts.

Block copolymer matrices are often used to control nanoparticle (NP) dispersion behavior, but the effects of diblock domain interfaces on particle-particle interactions have not been well characterized. In this paper, polymer field theoretic simulations are used to quantify interactions between both bare and grafted spherical NPs in microphase-separated A-B diblock copolymers. It is shown that for bare NPs that have an athermal interaction with and a diameter similar to the B domain, the presence of an A-B interface leads to an effective interaction between the particles with multiple minima separated by a free energy barrier. It is further shown that these effects primarily result from chain stretching and compression near the A-B interface induced by particle-particle interactions as opposed to increases in A-B contact at the interfaces. Grafted chains largely prevent these effects and reduce particle-particle interaction strength. When confined by diblock domain interfaces, grafted chains have a reduced extension compared to what is expected for de-wetted brush chains, as commonly described in homopolymer results. Finally, these studies indicate a new route toward linking spherical NPs in a controlled fashion, allowing for tunable plasmonic properties in the case of metallic NPs.

Field-Theoretic Simulations of the Distribution of Nanorods in Diblock Copolymer Thin Films.

Using block copolymer microphases to guide the self-assembly of nanorods in thin films can give rise to polymeric materials with unique optical, thermal, and mechanical properties beyond those found in neat block copolymers. Often the design and manufacture of these materials require exquisite control of the nanorod distribution, which is experimentally challenging due to the large parameter space spanned by this class of materials. Simulation approaches, on the other hand, can access the thermodynamics that contribute to the nanorod distribution and hence offer valuable guidance toward the design and manufacture of the materials. In this work, we employ complex Langevin field-theoretic simulations to examine the thermodynamic forces that govern the assembly of nanorods in thin films of block copolymers with a particular focus on vertically oriented cylindrical and lamellar domains. Our simulations show that the nanorod geometry, the substrate selectivity for the distinct blocks of the copolymer, and the film thickness all play important roles in engineering both the nanorod orientation and spatial distribution in diblock copolymer thin films. In addition, we employ thermodynamic integration to examine how the nanorods alter the stability of vertical and horizontal domains in thin films, where we find that the tendency of the nanorods to stabilize a vertical orientation depends on both the film thickness and the nanorod concentration.