Doped metal oxides are plasmonic materials that boast both synthetic and postsynthetic spectral tunability. They have already enabled promising smart window and optoelectronic technologies and have been proposed for use in surface enhanced infrared absorption spectroscopy (SEIRA) and sensing applications. Herein, we report the first step toward realization of the former utilizing cubic F and Sn codoped InO nanocrystals (NCs) to couple to the C-H vibration of surface-bound oleate ligands. Electron energy loss spectroscopy is used to map the strong near-field enhancement around these NCs that enables localized surface plasmon resonance (LSPR) coupling between adjacent nanocrystals and LSPR-molecular vibration coupling. Fourier transform infrared spectroscopy measurements and finite element simulations are applied to observe and explain the nature of the coupling phenomena, specifically addressing coupling in mesoscale assembled films. The Fano line shape signatures of LSPR-coupled molecular vibrations are rationalized with two-port temporal coupled mode theory. With this combined theoretical and experimental approach, we describe the influence of coupling strength and relative detuning between the molecular vibration and LSPR on the enhancement factor and further explain the basis of the observed Fano line shape by deconvoluting the combined response of the LSPR and molecular vibration in transmission, absorption and reflection. This study therefore illustrates various factors involved in determining the LSPR-LSPR and LSPR-molecular vibration coupling for metal oxide materials and provides a fundamental basis for the design of sensing or SEIRA substrates.

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For colloidal semiconductor nanocrystals (NCs), replacement of insulating organic capping ligands with chemically diverse inorganic clusters enables the development of functional solids in which adjacent NCs are strongly coupled. Yet controlled assembly methods are lacking to direct the arrangement of charged, inorganic cluster-capped NCs into open networks. Herein, we introduce coordination bonds between the clusters capping the NCs thus linking the NCs into highly open gel networks. As linking cations (Pt(2+)) are added to dilute (under 1 vol %) chalcogenidometallate-capped CdSe NC dispersions, the NCs first form clusters, then gels with viscoelastic properties. The phase behavior of the gels for variable [Pt(2+)] suggests they may represent nanoscale analogues of bridged particle gels, which have been observed to form in certain polymer colloidal suspensions.

We synthesized PbS/CdS core/shell quantum dots (QDs) to have functional single-emitter properties for room-temperature, solid-state operation in the telecom O and S bands. Two shell-growth methodscation exchange and successive ionic layer adsorption and reaction (SILAR)were employed to prepare QD heterostructures with shells of 2−16 monolayers. PbS/CdS QDs were sufficiently bright and stable to resolve photoluminescence (PL) spectra representing both bands from single nanocrystals using standard detection methods, and for a QD emitting in the O-band a second-order correlation function showed strong photon antibunching, important steps toward demonstrating the utility of lead chalcogenide QDs as single-photon emitters (SPEs). Irrespective of type, few telecom-SPEs exist that are capable of such room-temperature operation. Access to single-QD spectra enabled a direct assessment of spectral line width, which was ∼70−90 meV compared to much broader ensemble spectra (∼300 meV). We show inhomogeneous broadening results from dispersity in PbS core sizes that increases dramatically with extended cation exchange. Quantum yields (QYs) are negatively impacted at thick shells (>6 monolayers) and, especially, by SILAR-growth conditions. Time-resolved PL measurements revealed that, with SILAR, initially single-exponential PL-decays transition to biexponential, with opening of nonradiative carrier-recombination channels. Radiative decay times are, overall, longer for core/shell QDs compared to PbS cores, which we demonstrate can be partially attributed to some core/shell sizes occupying a quasi-type II electron−hole localization regime. Finally, we demonstrate that shell engineering and the use of lower laser-excitation powers can afford significantly suppressed blinking and photobleaching. However, dependence on shell thickness comes at a cost of less-than-optimal brightness, with implications for both materials and experimental design.

The presence of antimony, as a dopant in the colloidal growth reaction for CuIn(1-x)Ga(x)S2 (CIGS) nanocrystals, causes end-to-end fusion of nanorod pairs into nanodumbbells at high yield. The influence of the dopant on shape is indirect; antimony catalyzes the incorporation of gallium, which is found in high concentration at the junction between the fused nanorods.

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Stable, aqueous dispersions of nanoparticles based on the low band gap polymers poly [2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (APFO-3) and poly [N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) were prepared, using a flexible, surfactant-free reprecipitation method, and characterized by a variety of optical techniques. Light scattering measurements indicated average nanoparticle hydrodynamic diameters of approximately 40 nm. The particles presented wide-bandwidth absorption and photoluminescence excitation spectra with high absorption cross-sections on the order of 10(-12) cm(2). Nanoparticle emission spectra were significantly red-shifted, with decreased emission quantum yields and lifetimes, consistent with increased inter-polymer chain interactions in the condensed phase. Single particle photoluminescence studies highlighted the multi-chromophoric nature of the polymer nanoparticles and confirmed their favorable photostabilities. When the nanoparticles were doped with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), the correspondence of photoluminescence emission quenching, quantum yield decreases, emission lifetime shortening, and increased non-radiative rates with increasing PCBM concentration suggested efficient photo-induced donor-to-acceptor charge transfer between the conjugated polymers and the fullerene dopants co-localized in the nanoparticle cores. Taken together, the data suggest that these surfactant-free hybrid nanomaterials may be useful for integration with future nanostructured organic photovoltaics technologies.

Porous crystalline materials (PCMs) constitute a class of covalent or supramolecular coordination architectures having intensive application in the field of sensing, gas separation and storage, catalysis and optoelectronic device engineering....