Ordering of Polystyrene Nanoparticles on Substrates Pre-Coated with Different Polyelectrolyte Architectures

Adjusting the inter-particle distances in ordered nanoparticle arrays can create new nano-devices and is of increasing importance to a number of applications such as nanoelectronics and optical devices. The assembly of negatively charged polystyrene (PS) nanoparticles (NPs) on Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes, quaternized PDMAEMA brushes and Si/PEI/(PSS/PAH)2, was studied using dip- and spin-coating techniques. By dip-coating, two dimensional (2-D), randomly distributed non-close packed particle arrays were assembled on Si/PEI/(PSS/PAH)2 and PDMAEMA brushes. The inter-particle repulsion leads to lateral mobility of the particles on these surfaces. The 200 nm diameter PS NPs tended to an inter-particle distance of 350 to 400 nm (center to center). On quaternized PDMAEMA brushes, the strong attractive interaction between the NPs and the brush dominated, leading to clustering of the particles on the brush surface. Particle deposition using spin-coating at low spin rates resulted in hexagonal close-packed multilayer structures on Si/PEI/(PSS/PAH)2. Close-packed assemblies with more pronounced defects are also observed on PDMAEMA brushes and QPDMAEMA brushes. In contrast, randomly distributed monolayer NP arrays were achieved at higher spin rates on all polyelectrolyte architectures. The area fraction of the particles decreased with increasing spin rate

Article Ordering of Polystyrene Nanoparticles on Substrates Pre-Coated with Different Polyelectrolyte Architectures

Abstract: Adjusting the inter-particle distances in ordered nanoparticle arrays can create new nano-devices and is of increasing importance to a number of applications such as nanoelectronics and optical devices. The assembly of negatively charged polystyrene (PS) nanoparticles (NPs) on Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes, quaternized PDMAEMA brushes and Si/PEI/(PSS/PAH)2, was studied using dip- and spin-coating techniques. By dip-coating, two dimensional (2-D), randomly distributed non-close packed particle arrays were assembled on Si/PEI/(PSS/PAH)2 and PDMAEMA brushes. The inter-particle repulsion leads to lateral mobility of the particles on these surfaces. The 200 nm diameter PS NPs tended to an inter-particle distance of 350 to 400 nm (center to center). On quaternized PDMAEMA brushes, the strong attractive interaction between the NPs and the brush dominated, leading to clustering of the particles on the brush surface. Particle deposition using spin-coating at low spin rates resulted in hexagonal close-packed multilayer structures on Si/PEI/(PSS/PAH)2. Close-packed assemblies with more pronounced defects are also observed on PDMAEMA brushes and QPDMAEMA brushes. In contrast, randomly distributed monolayer NP arrays were achieved at higher spin rates on all polyelectrolyte architectures. The area fraction of the particles decreased with increasing spin rate. Int. J. Mol. Sci. 2013, 14 1289

Ordering of Polystyrene Nanoparticles on Substrates Pre-Coated with Different Polyelectrolyte Architectures

Adjusting the inter-particle distances in ordered nanoparticle arrays can create new nano-devices and is of increasing importance to a number of applications such as nanoelectronics and optical devices. The assembly of negatively charged polystyrene (PS) nanoparticles (NPs) on Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes, quaternized PDMAEMA brushes and Si/PEI/(PSS/PAH)2, was studied using dip- and spin-coating techniques. By dip-coating, two dimensional (2-D), randomly distributed non-close packed particle arrays were assembled on Si/PEI/(PSS/PAH)2 and PDMAEMA brushes. The inter-particle repulsion leads to lateral mobility of the particles on these surfaces. The 200 nm diameter PS NPs tended to an inter-particle distance of 350 to 400 nm (center to center). On quaternized PDMAEMA brushes, the strong attractive interaction between the NPs and the brush dominated, leading to clustering of the particles on the brush surface. Particle deposition using spin-coating at low spin rates resulted in hexagonal close-packed multilayer structures on Si/PEI/(PSS/PAH)2. Close-packed assemblies with more pronounced defects are also observed on PDMAEMA brushes and QPDMAEMA brushes. In contrast, randomly distributed monolayer NP arrays were achieved at higher spin rates on all polyelectrolyte architectures. The area fraction of the particles decreased with increasing spin rate

Stimuli-Responsive Polyelectrolyte Brushes As a Matrix for the Attachment of Gold Nanoparticles: The Effect of Brush Thickness on Particle Distribution

The effect of brush thickness on the loading of gold nanoparticles (AuNPs) within stimuli-responsive poly-(N,N-(dimethylamino ethyl) methacrylate) (PDMAEMA) polyelectrolyte brushes is reported. Atom transfer radical polymerization (ATRP) was used to grow polymer brushes via a “grafting from” approach. The brush thickness was tuned by varying the polymerization time. Using a new type of sealed reactor, thick brushes were synthesized. A systematic study was performed by varying a single parameter (brush thickness), while keeping all other parameters constant. AuNPs of 13 nm in diameter were attached by incubation. X-ray reflectivity, electron scanning microscopy and ellipsometry were used to study the particle loading, particle distribution and interpenetration of the particles within the brush matrix. A model for the structure of the brush/particle hybrids was derived. The particle number densities of attached AuNPs depend on the brush thickness, as do the optical properties of the hybrids. An increasing particle number density was found for increasing brush thickness, due to an increased surface roughness

Stimuli-Responsive Polyelectrolyte Brushes As a Matrix for the Attachment of Gold Nanoparticles: The Effect of Brush Thickness on Particle Distribution

The effect of brush thickness on the loading of gold nanoparticles (AuNPs) within stimuli-responsive poly-(N,N-(dimethylamino ethyl) methacrylate) (PDMAEMA) polyelectrolyte brushes is reported. Atom transfer radical polymerization (ATRP) was used to grow polymer brushes via a “grafting from” approach. The brush thickness was tuned by varying the polymerization time. Using a new type of sealed reactor, thick brushes were synthesized. A systematic study was performed by varying a single parameter (brush thickness), while keeping all other parameters constant. AuNPs of 13 nm in diameter were attached by incubation. X-ray reflectivity, electron scanning microscopy and ellipsometry were used to study the particle loading, particle distribution and interpenetration of the particles within the brush matrix. A model for the structure of the brush/particle hybrids was derived. The particle number densities of attached AuNPs depend on the brush thickness, as do the optical properties of the hybrids. An increasing particle number density was found for increasing brush thickness, due to an increased surface roughness

Brush/Gold Nanoparticle Hybrids: Effect of Grafting Density on the Particle Uptake and Distribution within Weak Polyelectrolyte Brushes

The effect of the brush grafting density on the loading of 13 nm gold nanoparticles (AuNPs) into stimuli-responsive poly­(<i>N</i>,<i>N</i>-(dimethylamino ethyl) methacrylate) (PDMAEMA) brushes anchored to flat impenetrable substrates is reported. Atom-transfer radical polymerization (ATRP) is used to grow polymer brushes via a “grafting from” approach from a 2-bromo-2-methyl-<i>N</i>-(3-(triethoxysilyl) propyl) propanamide (BTPAm)-covered silicon substrate. The grafting density is varied by using mixtures of initiator and a “dummy” molecule that is not able to initiate polymerization. A systematic study is carried out by varying the brush grafting density while keeping all of the other parameters constant. X-ray reflectivity is a suitable tool for investigating the spatial structure of the hybrid, and it is combined with scanning electron microscopy and UV/vis spectroscopy to study the particle loading and interpenetration of the particles within the polymer brush matrix. The particle uptake increases with decreasing grafting density and is highest for an intermediate grafting density because more space between the polymer chains is available. For very low grafting densities of PDMAEMA brushes, the particle uptake decreases because of a lack of the polymer matrix for the attachment of particles. The structure of the surface-grafted polymer chains changes after particle attachment. More water is incorporated into the brush matrix after particle immobilization, which leads to a swelling of the polymer chains in the hybrid material. Water can be removed from the brush by decreasing the relative humidity, which leads to brush shrinking and forces the AuNPs to get closer to each other