Control over Position, Orientation, and Spacing of Arrays of Gold Nanorods Using Chemically Nanopatterned Surfaces and Tailored Particle–Particle–Surface Interactions

Nepal, Dhriti; Önses, M. Serdar; Park, Kyoungweon; Jespersen, Michael L.; Thode, Christopher J.; Nealey, Paul F.; Vaia, Richard A.

doi:10.1021/nn301824u

Cited by 128 publications

(131 citation statements)

References 42 publications

(82 reference statements)

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“…Selective segregation of PGNPs at the interface or center of phase-separated block copolymer microdomains depends on the interplay between conformational and translational entropy of the system (6, 7). Considering the significant contribution of entropy in directed nanostructure formation (8,9), entropic interactions have the potential to tailor the organization of PGNPs within a chemically identical polymer matrix, which is not achievable by conventional techniques (10,11).…”

mentioning

confidence: 99%

Entropy-driven segregation of polymer-grafted nanoparticles under confinement

Zhang

Lee

Stafford

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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The modification of nanoparticles with polymer ligands has emerged as a versatile approach to control the interactions and organization of nanoparticles in polymer nanocomposite materials. Besides their technological significance, polymer-grafted nanoparticle (PGNP) dispersions have attracted interest as model systems to understand the role of entropy as a driving force for microstructure formation. For instance, densely and sparsely grafted nanoparticles show distinct dispersion and assembly behaviors within polymer matrices due to the entropy variation associated with conformational changes in brush and matrix chains. Here we demonstrate how this entropy change can be harnessed to drive PGNPs into spatially organized domain structures on submicrometer scale within topographically patterned thin films. This selective segregation of PGNPs is induced by the conformational entropy penalty arising from local perturbations of grafted and matrix chains under confinement. The efficiency of this particle segregation process within patterned mesa−trench films can be tuned by changing the relative entropic confinement effects on grafted and matrix chains. The versatility of topographic patterning, combined with the compatibility with a wide range of nanoparticle and polymeric materials, renders SCPINS (soft-confinement pattern-induced nanoparticle segregation) an attractive method for fabricating nanostructured hybrid films with potential applications in nanomaterial-based technologies.polymer thin film | polymer-grafted nanoparticle | entropy | confinement | topographic pattern T he dispersion and organization of nanoparticles in polymeric matrices are important to improve the properties of polymer nanocomposite materials (1, 2). Polymer-grafted nanoparticles (PGNPs) have attracted much attention in this regard due to their enhanced miscibility and versatility of assembled structures in polymeric materials via interacting grafted polymer layers (3, 4). The cloaking of nanoparticles by densely grafted polymer layers with the same chemical composition as the matrix leads to an "athermal" particle−polymer blend where entropic interactions dominate the thermodynamics of the system (5). Selective segregation of PGNPs at the interface or center of phase-separated block copolymer microdomains depends on the interplay between conformational and translational entropy of the system (6, 7). Considering the significant contribution of entropy in directed nanostructure formation (8, 9), entropic interactions have the potential to tailor the organization of PGNPs within a chemically identical polymer matrix, which is not achievable by conventional techniques (10, 11).The entropic effects can be magnified by confining PGNPs in thin-film geometries. Under confinement, the conformation of the grafted chains is altered, and the associated entropic penalty could drive directional migration of PGNPs and potentially generate visually ordered microstructures. To illustrate this concept, we introduce lateral confinement contrast by topographi...

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confidence: 99%

Entropy-driven segregation of polymer-grafted nanoparticles under confinement

Zhang

Lee

Stafford

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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“…10 Selective chemical modification of the ends of the NRs, albeit synthetically nontrivial, is perhaps among the most successful approaches toward the creation of long chains of end-to-end NR assembly. 21,29 Prefabricated templates 35,36 or structural frameworks formed from the self-assembly of a block copolymer (BCP) 37 have been used to confine spherical nanoparticles or NRs to form one-dimensional (1D) or two-dimensional (2D) arrays. BCPbased supramolecules are effective in this as well.…”

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confidence: 99%

End-to-End Alignment of Nanorods in Thin Films

Thorkelsson¹,

Nelson²,

Alivisatos

et al. 2013

Nano Lett.

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A simple approach to obtain end-to-end assemblies of nanorods over macroscopic distances in thin films is described. Nanorods with aspect ratio of 8−12 can be aligned parallel to the surface in an end-to-end fashion by imposing geometric confinement via block copolymer-based supramolecular assemblies. Successful control over the orientation and location of nanorods requires a balance of particle−particle interactions and entropy associated with geometric confinement from the supramolecular framework, as well as consideration of the kinetics of assembly.

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“…A significant effort has been devoted to the self-assembly of Au NRs through blockcopolymer-templating methods [7][8][9][10]. Liu et al used the following three steps to align Au NRs on block copolymer templates: (i) Approximately 100 nm-thick polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) block copolymer films were prepared by spin coating on silicon wafers [9].…”

Section: Introductionmentioning

confidence: 99%

Alignment of Gold Nanorods in Directionally Solidified Polymer Blends

Ejima

Sakurai

Yoshie

2017

J. Photopol. Sci. Technol.

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We studied the alignment of gold nanorods (Au NRs) in polymer blends that were directionally solidified in the crystallizable organic solvent trichlorobenzene (TCB). The polymer blends/Au NRs were dissolved or dispersed in TCB at 80 °C between two glass plates. By cooling the sample, the polymer blends and Au NRs were directionally solidified as the liquid TCB transformed into large single crystals. With poly(3-hexylthiophene-2,5-diyl)/polyethylene glycol (P3HT/PEG) used as the polymer blend pair, PEG-modified Au NRs predominantly localized inside the PEG domains of the solidified films. In contrast, with a P3HT/poly(2-vinylpyridine) blend, PEG-modified Au NRs mostly localized at the interface between the polymers. These results show that directional solidification in crystallizable organic solvents is an effective one-step process for the alignment of Au NRs in polymer matrices.

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Control over Position, Orientation, and Spacing of Arrays of Gold Nanorods Using Chemically Nanopatterned Surfaces and Tailored Particle–Particle–Surface Interactions

Cited by 128 publications

References 42 publications

Entropy-driven segregation of polymer-grafted nanoparticles under confinement

Entropy-driven segregation of polymer-grafted nanoparticles under confinement

End-to-End Alignment of Nanorods in Thin Films

Alignment of Gold Nanorods in Directionally Solidified Polymer Blends

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