Hierarchical Assembly of Nanoparticle Superstructures from Block Copolymer-Nanoparticle Composites

Kang, Huiman; Detcheverry, François; Mangham, Andrew N.; Stoykovich, Mark P.; Daoulas, Kostas Ch.; Hamers, Robert J.; Müller, Marcus; Pablo, Juan J. de; Nealey, Paul F.

doi:10.1103/physrevlett.100.148303

Cited by 137 publications

(102 citation statements)

References 27 publications

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“…In addition, the ability to synthesize homogenous or combinatorial arrays of nanoparticles on surfaces with control over individual particle composition and size will enable important fundamental studies and technological applications in fields spanning catalysis, nanomagnetism, microelectronics, and plasmonics. Finally, the pathway-dependent observations pertaining to these polymer nanoreactors likely will extend to other block copolymer-mediated particle syntheses, including ones that target 2D-and 3D-latticed structures (30)(31)(32).…”

Section: Resultsmentioning

confidence: 99%

Delineating the pathways for the site-directed synthesis of individual nanoparticles on surfaces

Liu

Eichelsdoerfer²,

Rasin

et al. 2012

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

111

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Although nanoparticles with exquisite properties have been synthesized for a variety of applications, their incorporation into functional devices is challenging owing to the difficulty in positioning them at specified sites on surfaces. In contrast with the conventional synthesis-then-assembly paradigm, scanning probe block copolymer lithography can pattern precursor materials embedded in a polymer matrix and synthesize desired nanoparticles on site, offering great promise for incorporating nanoparticles into devices. This technique, however, is extremely limited from a materials standpoint. To develop a materials-general method for synthesizing nanoparticles on surfaces for broader applications, a mechanistic understanding of polymer-mediated nanoparticle formation is crucial. Here, we design a four-step synthetic process that enables independent study of the two most critical steps for synthesizing single nanoparticles on surfaces: phase separation of precursors and particle formation. Using this process, we elucidate the importance of the polymer matrix in the diffusion of metal precursors to form a single nanoparticle and the three pathways that the precursors undergo to form nanoparticles. Based on this mechanistic understanding, the synthetic process is generalized to create metal (Au, Ag, Pt, and Pd), metal oxide (Fe 2 O 3 , Co 2 O 3 , NiO, and CuO), and alloy (AuAg) nanoparticles. This mechanistic understanding and resulting process represent a major advance in scanning probe lithography as a tool to generate patterns of tailored nanoparticles for integration with solid-state devices.T he integration of nanoparticles into devices has enabled applications spanning sensing (1, 2), catalysis (3), electronics (2), photonics (4), and plasmonics (5, 6), but synthesizing individual nanoparticles with control over size, composition, and placement on substrates is challenging (1-3, 6, 7). With conventional approaches, nanoparticles are synthesized and subsequently positioned on a surface using techniques such as parallel printing (8), surface dewetting (9, 10), microdroplet molding (7), nanoparticle sliding (11), direct writing (4, 12, 13), and self-assembly (2, 14, 15). However, it is difficult and in most cases, impossible to use these methods to reliably make and position a single particle on a surface with nanometer-scale control.In contrast with the conventional synthesis-then-positioning paradigm, which is the basis for most single-particle device incorporation schemes, scanning probe block copolymer lithography (SPBCL) is an example of precursor positioning-then-synthesis. The technique uses concepts from the block copolymer community (16) and the positional control offered by dip-pen nanolithography (DPN) (17) to deliver attoliter volumes of a metalcoordinated block copolymer onto a surface, which then can be used to synthesize individual nanoparticles (18,19). Importantly, SPBCL allows one to directly synthesize arbitrary patterns of single nanoparticles over large areas on a surface, which has been usef...

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Section: Resultsmentioning

confidence: 99%

Delineating the pathways for the site-directed synthesis of individual nanoparticles on surfaces

Liu

Eichelsdoerfer²,

Rasin

et al. 2012

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

111

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“…In both cases a bimodal distribution of nanoparticles at the block interfaces was calculated, due to density changes in the polymer film. 182 Li et al used self assembly of Au nanoparticles in the P4VP domains of a PS-b-P4VP diblock copolymer spherical monolayer thin film to measure the collective electron transport behavior of the confined particles, and found an increased electron tunneling rate constant as compared to nanoparticles which were freely dispersed in a P4VP homopolymer thin film.…”

Section: 177mentioning

confidence: 99%

Thin films of complexed block copolymers

2009

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Due to their ability to microphase separate into well ordered structures with periodicities on the nanometre scale, block copolymers have received widespread attention as building blocks for the fabrication of nanomaterials. In particular, thin films of block copolymers promise new technological breakthroughs in e.g. computer memory applications. This Review gives a short overview of progress that has been made in preparing suitable thin films of conventional coil-coil diblock copolymer systems, while the advantages as well as the complexities of using more unconventional systems such as triblock copolymers and supramolecular systems are emphasized. Gerrit tenBrinke obtained his PhD in Statistical Physics from the University of Groningen, The Netherlands. He spent two years as a postdoctoral fellow at the University of Massachusetts at Amherst. In 1985 he became Associate Professor in the Polymer Department of the University of Groningen and in 1996 Professor. During 1994-1999 he was also part time Professor at the Helsinki University of Technology working closely together with Olli Ikkala. His research interests are self-assembly in complex polymer systems.

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“…Specific recognition and binding events, such as DNA hybridization and protein folding, are based on collective and cooperative multiple secondary interactions. More recently, anisotropy in shape has also been recognized as a critical factor in the self-assembly process due to packing constraints (17)(18)(19)(20)(21)(22), as indicated by the emerging concept of "shape amphiphiles" (23,24). However, it remains challenging to design nanomaterials "from scratch" (25) that can generate diverse structures at a specific length scale, e.g., the nanostructures with feature sizes around 10 nm or smaller.…”

mentioning

confidence: 99%

Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering

Yue

Hsieh

et al. 2013

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

202

163

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The engineering of structures across different length scales is central to the design of novel materials with controlled macroscopic properties. Herein, we introduce a unique class of self-assembling materials, which are built upon shape-and volume-persistent molecular nanoparticles and other structural motifs, such as polymers, and can be viewed as a size-amplified version of the corresponding small-molecule counterparts. Among them, "giant surfactants" with precise molecular structures have been synthesized by "clicking" compact and polar molecular nanoparticles to flexible polymer tails of various composition and architecture at specific sites. Capturing the structural features of small-molecule surfactants but possessing much larger sizes, giant surfactants bridge the gap between small-molecule surfactants and block copolymers and demonstrate a duality of both materials in terms of their self-assembly behaviors. The controlled structural variations of these giant surfactants through precision synthesis further reveal that their selfassemblies are remarkably sensitive to primary chemical structures, leading to highly diverse, thermodynamically stable nanostructures with feature sizes around 10 nm or smaller in the bulk, thin-film, and solution states, as dictated by the collective physical interactions and geometric constraints. The results suggest that this class of materials provides a versatile platform for engineering nanostructures with sub-10-nm feature sizes. These findings are not only scientifically intriguing in understanding the chemical and physical principles of the self-assembly, but also technologically relevant, such as in nanopatterning technology and microelectronics. giant molecules | shape amphiphiles | hybrid materials | microphase separation | colloidal particles P hysical properties of materials are dictated by the hierarchical arrangements of atoms, molecules, and supramolecular assemblies across different length scales. The construction and engineering of structures at each length scale, especially at the 2-to 100-nm scale (1), are critically important in achieving desired macroscopic properties. As the traditional top-down lithography techniques face serious challenges in fabricating 2D and 3D nanostructured materials with sub-20-nm feature sizes (2), the bottom-up approach based on self-organization or directed assembly of functional molecules provides a promising alternative. The past decades have witnessed the development of diverse self-assembly building blocks ranging from small-molecule surfactants (3), block copolymers (4), and dendrimers (5) to DNAs (6, 7), peptides (8), and proteins (9). Notably, these motifs have enabled the programmed self-assembly of nanomaterials as demonstrated in DNA-coated nanoparticles (10-13). These studies have greatly improved our understanding of the thermodynamics and kinetics of self-assembly processes and opened enormous possibilities in modern nanotechnology.Noncovalent interactions, such as hydrogen bonding, amphiphilic effect, π-π interacti...

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Hierarchical Assembly of Nanoparticle Superstructures from Block Copolymer-Nanoparticle Composites

Cited by 137 publications

References 27 publications

Delineating the pathways for the site-directed synthesis of individual nanoparticles on surfaces

Delineating the pathways for the site-directed synthesis of individual nanoparticles on surfaces

Thin films of complexed block copolymers

Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering

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