A Tunable Polymer-Metal Based Anti-Reflective Metasurface.

Anti-reflective surfaces are of great interest for optical devices, sensing, photovoltaics, and photocatalysis. However, most of the anti-reflective surfaces lack in situ tunability of the extinction with respect to wavelength. This communication demonstrates a tunable anti-reflective surface based on colloidal particles comprising a metal core with an electrochromic polymer shell. Random deposition of these particles on a reflective surface results in a decrease in the reflectance of up to 99.8% at the localized surface plasmon resonance frequency. This narrow band feature can be tuned by varying the pH or by application of an electric potential, resulting in wavelength shifts of up to 30 nm. Electrophoretic particle deposition is shown to be an efficient method for controlling the interparticle distance and thereby further optimizing the overall efficiency of the anti-reflective metasurface.

Plasmonic gold-poly(N-isopropylacrylamide) core-shell colloids with homogeneous density profiles: a small angle scattering study.

Coating metal nanocrystals with responsive polymers provides a model case of smart, functional materials, where the optical properties can be modulated by external stimuli. However the optical response is highly sensitive to the polymer shell morphology, thickness and dielectric contrast. In this paper we study the nature of cross-linked, thermoresponsive polymer shells for the first time using four different scattering approaches to elucidate the density profile of the shells. Each scattering method provides unique information about the temperature-induced changes of shell thickness in terms of hydrodynamic radius and radius of gyration, the pair-distance distribution functions of the shells as well as the dynamic network fluctuations. Only a combination of these different scattering techniques allows to develop a morphological model of the core-shell particles. We further demonstrate control of the cross-linker distribution in core-shell synthesis by semi-batch precipitation copolymerization. Conducting the polymerization in three steps, we show for the first time that the polymer shell thickness can be successively increased without affecting the shell morphology and response behavior.

Surface plasmon coupling in end-to-end linked gold nanorod dimers and trimers.

Colloidal gold nanorods were aligned end-to-end via dithiol coupling. The scattering properties of the resultant nanostructures were investigated at the single particle level by combining dark-field microscopy and high resolution scanning electron microscopy. The longitudinal surface plasmon resonance of end-to-end coupled Au nanorods exhibited a red-shift as the number of rods in the chain increased. The nanostructures exhibited polarization-dependent optical properties, due to selective excitation of collective bonding and anti-bonding modes. The surface plasmon peak energy was not strongly dependent on the angle of rod-sphere-rod trimers. The experimental scattering spectra were compared with the results obtained from theoretical calculations using the Finite Element Method (FEM) and found to be in good agreement.

Single-photon emission and quantum characterization of zinc oxide defects.

Room temperature single-photon emission and quantum characterization is reported for isolated defects in zinc oxide. The defects are observed in thin films of both in-house synthesized and commercial zinc oxide nanoparticles. Emission spectra in the red and infrared, second-order photon correlation functions, lifetime measurements, and photon count rates are presented. Both two- and three-state emitters are identified. Sub-band gap absorption and red emission suggest these defects are the zinc vacancy. These results identify a new source of single photons in a readily available wide band gap semiconductor material which has exceptional electrical, optical, and biocompatibility properties.

Solution-processed sintered nanocrystal solar cells via layer-by-layer assembly.

Solar cells made by high temperature and vacuum processes from inorganic semiconductors are at a perceived cost disadvantage when compared with solution-processed systems such as organic and dye-sensitized solar cells. We demonstrate that totally solution processable solar cells can be fabricated from inorganic nanocrystal inks in air at temperature as low as 300 °C. Focusing on a CdTe/ZnO thin-film system, we report solar cells that achieve power conversion efficiencies of 6.9% with greater than 90% internal quantum efficiency. In our approach, nanocrystals are deposited from solution in a layer-by-layer process. Chemical and thermal treatments between layers induce large scale grain formation, turning the 4 nm CdTe particles into pinhole-free films with an optimized average crystallite size of ∼70 nm. Through capacitance-voltage measurements we demonstrate that the CdTe layer is fully depleted which enables the charge carrier collection to be maximized.

Cells as factories for humanized encapsulation.

Biocompatibility is of paramount importance for drug delivery, tumor labeling, and in vivo application of nanoscale bioprobes. Until now, biocompatible surface processing has typically relied on PEGylation and other surface coatings, which, however, cannot minimize clearance by macrophages or the renal system but may also increase the risk of chemical side effects. Cell membranes provide a generic and far more natural approach to the challenges of encapsulation and delivery in vivo. Here we harness for the first time living cells as "factories" to manufacture cell membrane capsules for encapsulation and delivery of drugs, nanoparticles, and other biolabels. Furthermore, we demonstrate that the built-in protein channels of the new capsules can be utilized for controlled release of encapsulated reagents.

Polymer-coated nanoparticles: a universal tool for biolabelling experiments.

Water solubilization of nanoparticles is a fundamental prerequisite for many biological applications. To date, no single method has emerged as ideal, and several different approaches have been successfully utilized. These 'phase-transfer' strategies are reviewed, indicating key advantages and disadvantages, and a discussion of conjugation strategies is presented. Coating of hydrophobic nanoparticles with amphiphilic polymers provides a generic pathway for the phase transfer of semiconductor, magnetic, metallic, and upconverting nanoparticles from nonpolar to polar environments. Amphiphilic polymers that include maleimide groups can be readily functionalized with chemical groups for specific applications. In the second, experimental part, some of the new chemical features of such polymer-capped nanoparticles are demonstrated. In particular, nanoparticles to which a pH sensitive fluorophore has been attached are described, and their use for intracellular pH-sensing demonstrated. It is shown that the properties of analyte-sensitive fluorophores can be tuned by using interactions with the underlying nanoparticles.

Surface plasmon spectroscopy of gold-poly-N-isopropylacrylamide core-shell particles.

Highly uniform, core-shell microgels consisting of single gold nanoparticle cores and cross-linked poly-N-isopropylacrylamide (PNIPAM) shells were prepared by a novel, versatile protocol. The synthetic pathway allows control over the polymer shell thickness and its swelling behavior. The core-shell structure was investigated by electron microscopy and atomic force microscopy, whereas the swelling behavior of the shell was studied by means of dynamic light scattering and UV-vis spectroscopy. Furthermore, the latter method was used to investigate the optical properties of the hybrid particles. By modeling the scattering contribution from the PNIPAM shells, the absorption spectra of the gold nanoparticle cores could be recovered. This allows the particle concentration to be determined, and this in turn permits the calculation of the molar mass of the hybrid particles as well as the refractive index of the shells.

2D assembly of gold-PNIPAM core-shell nanocrystals.

2D arrays of Au-PNIPAM core-shell nanocrystals were fabricated using convective deposition and spin-coating. The particle density and ordering were studied by AFM. Annealing at 700 °C removes the polymer shell, while retaining a monolayer of well-separated gold nanoparticles. The surface plasmon modes of the colloid monolayers could be measured by spectroscopic ellipsometry.

Hydrogen-bond-selective phase transfer of nanoparticles across liquid/gel interfaces.

In the swim: Colloidal nanoparticles coated with polylactide (PLA, red) and poly(ethylene glycol) brushes (PEG, black) can transfer from organic to aqueous phases across liquid/liquid or liquid/gel interfaces during degradation of the PLA coating (see picture: first step), which is driven selectively by the hydrogen bonding of the PEG coating with the aqueous phase (second step).

Dielectrophoresis-Raman spectroscopy system for analysing suspended nanoparticles.

A microfluidic dielectrophoresis platform consisting of curved microelectrodes was developed and integrated with a Raman spectroscopy system. The electrodes were patterned on a quartz substrate, which has insignificant Raman response, and integrated with a microfluidic channel that was imprinted in poly-dimethylsiloxane (PDMS). We will show that this novel integrated system can be efficiently used for the determination of suspended particle types and the direct mapping of their spatial concentrations. We will also illustrate the system's unique advantages over conventional optical systems. Nanoparticles of tungsten trioxide (WO(3)) and polystyrene were used in the investigations, as they are Raman active and can be homogeneously suspended in water.

The preparation of colloidally stable, water-soluble, biocompatible, semiconductor nanocrystals with a small hydrodynamic diameter.

We report a simple, economical method for generating water-soluble, biocompatible nanocrystals that are colloidally robust and have a small hydrodynamic diameter. The nanocrystal phase transfer technique utilizes a low molecular weight amphiphilic polymer that is formed via maleic anhydride coupling of poly(styrene-co-maleic anhydride) with either ethanolamine or Jeffamine M-1000 polyetheramine. The polymer encapsulated water-soluble nanocrystals exhibit the same optical spectra as those formed initially in organic solvents, preserve photoluminescence intensities, are colloidally stable over a wide pH range (pH 3-13), have a small hydrodynamic diameter, and exhibit low levels of nonspecific binding to cells.

Experimental determination of quantum dot size distributions, ligand packing densities, and bioconjugation using analytical ultracentrifugation.

Analytical ultracentrifugation (AUC) was used to characterize the size distribution and surface chemistry of quantum dots (QDs). AUC was found to be highly sensitive to nanocrystal size, resolving nanocrystal sizes that differ by a single lattice plane. Sedimentation velocity data were used to calculate the ligand packing density at the crystal surface for different sized nanocrystals. Dihydrolipoic acid poly(ethylene glycol) was found to bind between 66 and 60% of the surface cadmium atoms for CdSe nanocrystals in the 1.54-2.59 nm radius size regime. The surface ligand chemistry was found to affect QD sedimentation, with larger ligands decreasing the sedimentation rate through an increase in particle volume and increase in frictional coefficient. Finally, AUC was used to detect and analyze protein association to QDs. Addition of bovine serum albumin (BSA) to the QD sample resulted in a reduced sedimentation rate, which may be attributed to an associated frictional drag. We calculated that one to two BSA molecules bind per QD with an associated frictional ratio of 1.2.