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A variety of optical applications rely on the absorption and reemission of light. The quantum yield of this process often plays an essential role. When the quantum yield deviates from unity by significantly less than 1%, applications such as luminescent concentrators and optical refrigerators become possible. To evaluate such high performance, we develop a measurement technique for luminescence efficiency with sufficient accuracy below one part per thousand. Photothermal threshold quantum yield is based on the quantization of light to minimize overall measurement uncertainty. This technique is used to guide a procedure capable of making ensembles of near-unity emitting cadmium selenide/cadmium sulfide (CdSe/CdS) core-shell quantum dots. We obtain a photothermal threshold quantum yield luminescence efficiency of 99.6 ± 0.2%, indicating nearly complete suppression of nonradiative decay channels.

Charge transport in conjugated polymer semiconductors has traditionally been thought to be limited to a low-mobility regime by pronounced energetic disorder. Much progress has recently been made in advancing carrier mobilities in field-effect transistors through developing low-disorder conjugated polymers. However, in diodes these polymers have to date not shown much improved mobilities, presumably reflecting the fact that in diodes lower carrier concentrations are available to fill up residual tail states in the density of states. Here, we show that the bulk charge transport in low-disorder polymers is limited by water-induced trap states and that their concentration can be dramatically reduced through incorporating small molecular additives into the polymer film. Upon incorporation of the additives we achieve space-charge limited current characteristics that resemble molecular single crystals such as rubrene with high, trap-free SCLC mobilities up to 0.2 cm2/Vs and a width of the residual tail state distribution comparable to kBT.

Disk-shaped molecules with large aromatic π-surfaces are a class of organic semiconductors in which the charge-carrier transport properties could be greatly facilitated by preferred intermolecular stacking of the π-surfaces. The optical and electronic properties are not only determined by the core aromatic structure of these disk-shaped molecules but are also strongly dependent on the side chains, which directly impact the molecular self-assembly behavior in condensed phases. Triphenylene-tris(naphthaleneimidazole) (TP-TNI) is a recently reported n-type semiconductor featuring a large π-core and branched side chains, with an electron-transporting mobility reaching 10-4 cm2 V-1 s-1. To further improve material performance, a detailed study is needed to understand the dependence of carrier transport properties on both the core electronic structure and side chain. Here, we present the detailed synthesis and characterization of a TP-TNI derivative bearing linear side chains, which has demonstrated a field-effect electron-transport mobility of up to 1.3 × 10-3 cm2 V-1 s-1. The more than 1 order improvement in electron-transport properties over the branched side chain homologue can be correlated to ordered twisted packing in the thin film, as revealed by in situ variable temperature grazing incidence wide-angle X-ray scattering studies. In-depth theoretical understanding of the frontier orbitals, reorganization energies, and charge-transfer integrals of TP-TNI molecules has provided further insight into the relationship between the molecular stacking geometry and charge-transport properties.

We fabricate a field-effect transistor by covalently functionalizing PbS nanoparticles with tetrathiafulvalenetetracarboxylate. Following experimental results from cyclic voltammetry and ambient-pressure X-ray photoelectron spectroscopy, we postulate a near-resonant alignment of the PbS 1Sh state and the organic HOMO, which is confirmed by atomistic calculations. Considering the large width of interparticle spacing, we observe an abnormally high field-effect hole mobility, which we attribute to the postulated resonance. In contrast to nanoparticle devices coupled through common short-chained ligands, our system maintains a large degree of macroscopic order as revealed by X-ray scattering. This provides a different approach to the design of hybrid organic-inorganic nanomaterials, circumvents the problem of phase segregation, and holds for versatile ways to design ordered, coupled nanoparticle thin films.

We fabricate a field-effect transistor by covalently functionalizing PbS nanoparticles with tetrathiafulvalenetetracarboxylate. Following experimental results from cyclic voltammetry and ambient-pressure X-ray photoelectron spectroscopy, we postulate a near-resonant alignment of the PbS 1Sh state and the organic HOMO, which is confirmed by atomistic calculations. Considering the large width of interparticle spacing, we observe an abnormally high field-effect hole mobility, which we attribute to the postulated resonance. In contrast to nanoparticle devices coupled through common short-chained ligands, our system maintains a large degree of macroscopic order as revealed by X-ray scattering. This provides a different approach to the design of hybrid organic-inorganic nanomaterials, circumvents the problem of phase segregation, and holds for versatile ways to design ordered, coupled nanoparticle thin films.

Isotopic substitution is a useful method to study the influence of nuclear motion on the kinetics of charge transport in semiconductors. However, in organic semiconductors, no observable isotope effect on field‐effect mobility has been reported. To understand the charge transport mechanism in rubrene, the benchmark organic semiconductor, crystals of fully isotopically substituted rubrene, 13C‐rubrene (13C42H28), are synthesized and characterized. Vapor‐grown 13C‐rubrene single crystals have the same crystal structure and quality as native rubrene crystals (i.e., rubrene with a natural abundance of carbon isotopes). The characteristic transport signatures of rubrene, including room temperature hole mobility over 10 cm2 V−1 s−1, intrinsic band‐like transport, and clear Hall behavior in the accumulation layer of air‐gap transistors, are also observed for 13C‐rubrene crystals. The field‐effect mobility distributions based on 74 rubrene and 13C‐rubrene devices, respectively, reveal that 13C isotopic substitution produces a 13% reduction in the hole mobility of rubrene. The origin of the negative isotope effect is linked to the redshift of vibrational frequencies after 13C‐substitution, as demonstrated by computer simulations based on the transient localization (dynamic disorder) scenario. Overall, the data and analysis provide an important benchmark for ongoing efforts to understand transport in ordered organic semiconductors. [ABSTRACT FROM AUTHOR]

Ladder-type oligophenylenes (LOPP) with bridging heteroatoms are interesting systems as they offer novel electronic and photophysical properties on account of the rigid structural features, more efficient electron delocalization on the coplanar aromatic framework, and strong intermolecular interactions. LOPPs incorporating multiple phosphorous centers combine the excellent electronic properties of phospholes and rigidified conjugated framework of LOPPs, thus positioning themselves as an attractive class of organic semiconductors. To date, there still lacks an effective synthetic methodology towards LOPPs with multiple phosphorous bridges. Herein, we describe the synthesis and properties of a new class of bisphosphole-bridged ladder oligo( p-phenylene)s and the related phosphoxides. The synthesis of phospholes was achieved by a four-fold free-radical phosphanylation reaction of a tetrabromo p-terphenylene or biphenyl-thiophene. Sequential trapping of four highly reactive aryl radicals occurred effectively to give the desired phosphorous-containing ladder compound. The oxides of the phospholes are shown to be strong fluorophores that can be used as potential n-type building blocks for organic semiconducting materials. [ABSTRACT FROM AUTHOR]

Encaged! Three-terminal interlocked molecular species were obtained by dynamic (2+3) assembly of a cagelike macro-bicycle around a trifurcated trispyridinium π guest. The complex is stabilized by π-π interactions and multiple [C-H⋅⋅⋅O] and [C-H⋅⋅⋅N] interactions. Uncomplexed guest molecules cocrystallize alongside the threaded complexes in the solid state, thus giving extended π-stacked columns., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)