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Title: Directionally Interacting Spheres and Rods Form Ordered Phases

Journal Article · · ACS Nano
 [1]; ORCiD logo [2];  [3]; ORCiD logo [2]; ORCiD logo [4]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  2. Princeton Univ., NJ (United States). Dept. of Chemical and Biological Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering, Dept. of Applied Physics and Applied Mathematics
  4. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering

The structures formed by mixtures of dissimilarly shaped nanoscale objects can significantly enhance our ability to produce nanoscale architectures. However, understanding their formation is a complex problem due to the interplay of geometric effects (entropy) and energetic interactions at the nanoscale. Spheres and rods are perhaps the most basic geometrical shapes and serve as convenient models of such dissimilar objects. The ordered phases formed by each of these individual shapes have already been explored, but, when mixed, spheres and rods have demonstrated only limited structural organization to date. We show using experiments and theory that the introduction of directional attractions between rod ends and isotropically interacting spherical nanoparticles (NPs) through DNA base pairing leads to the formation of ordered three-dimensional lattices. The spheres and rods arrange themselves in a complex alternating manner, where the spheres can form either a face-centered cubic (FCC) or hexagonal close-packed (HCP) lattice, or a disordered phase, as observed by in situ X-ray scattering. Increasing NP diameter at fixed rod length yields an initial transition from a disordered phase to the HCP crystal, energetically stabilized by rod-rod attraction across alternating crystal layers, as revealed by theory. In the limit of large NPs, the FCC structure is instead stabilized over the HCP by rod entropy. Thus, we propose that directionally specific attractions in mixtures of anisotropic and isotropic objects offer insight into unexplored self-assembly behavior of noncomplementary shaped particles.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1399671
Report Number(s):
BNL-114380-2017-JA; KC0403020
Journal Information:
ACS Nano, Vol. 11, Issue 5; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

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Cited By (6)

Self-assembly as a key player for materials nanoarchitectonics journal January 2019
DNA nanostructure-directed assembly of metal nanoparticle superlattices journal April 2018
Limiting the valence: advancements and new perspectives on patchy colloids, soft functionalized nanoparticles and biomolecules journal January 2017
How to simulate patchy particles journal May 2018
Monte Carlo simulation of cylinders with short-range attractions journal September 2018
How to Simulate Patchy Particles preprint January 2018