Journal
ACS NANO
Volume 14, Issue 8, Pages 9644-9651Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.0c00668
Keywords
polymer-grafted nanoparticles; effective softness; self-assembly; polymer ligand; body-centered tetragonal
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Funding
- National Research Foundation (NRF) Grant - Korean Government [NRF-2020M3H4A1A01086888, 2017M3D1A1039553, 2020M31A210101310, 2019R1I1A1A01058781]
- Research Projects of the KAIST-KUSTAR
- TJ Park Science Fellowship of POSCO TJ Park Foundation
- National Science Foundation [NSF DMR 1905487]
- National Research Foundation of Korea [2019R1I1A1A01058781] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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Achieving ordered arrays of nanoparticles (NPs) with controlled packing symmetry and interparticle spacing is of great importance to design complex metamaterials. Herein, we report softness- and size-dependent self-assembly behavior of polystyrene-grafted Au NPs (Au@PS NPs). We varied the core size of Au NPs from 1.9 to 9.6 nm and the number-average molecular weight (M-n) of thiol-terminated polystyrene from 1.8 to 7.9 kg mol(-1). The optimal packing model based on an effective softness parameter lambda(eff) that accounts for close-packed and semidilute brush regimes could predict the effective radius of Au@PS NPs (within +/- 9%) for a wide range of PS M-n, grafting density, and Au core size. With increasing lambda(eff), the self-assembled Au@PS NP superlattices undergo a symmetry transition from hexagonal dose packed (hcp) to body-centered tetragonal (bct) to body-centered cubic (bcc). This work demonstrates the effective softness model as a simple but robust tool for the design of NP superlattices with precisely controlled interparticle distance and packing symmetry, both of which are critical for the development of sophisticated materials through control of nanoscale structure.
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