Star-shaped and linear π-conjugated oligomers consisting of a tetrathienoanthracene core and multiple diketopyrrolopyrrole arms for organic solar cells.

Solution-processable star-shaped and linear π-conjugated oligomers consisting of an electron-donating tetrathienoanthracene (TTA) core and electron-accepting diketopyrrolopyrrole (DPP) arms, namely, TTA-DPP4 and TTA-DPP2, were designed and synthesized. Based on density functional theory calculations, the star-shaped TTA-DPP4 has a larger oscillator strength than the linear TTA-DPP2, and consequently, better photoabsorption property over a wide range of visible wavelengths. The photovoltaic properties of organic solar cells based on TTA-DPP4 and TTA-DPP2 with a fullerene derivative were evaluated by varying the thickness of the bulk heterojunction active layer. As a result of the enhanced visible absorption properties of the star-shaped π-conjugated structure, better photovoltaic performances were obtained with relatively thin active layers (40-60 nm).

Metal nanodot arrays fabricated via seed-mediated electroless plating with block copolymer thin film scaffolding.

We present an alternative approach to fabricating hexagonally arranged nanodot arrays of various metals by seed-mediated electroless plating with a cylinder-forming block copolymer thin film, PEO-b-PMA(Az), as a scaffold. Metal ions were selectively incorporated into PEO cylinders, followed by their reduction to metal and the etching of the scaffold to obtain highly ordered seed arrays of Au, Pd, and Pt. Nanodot arrays of the target metals (Au, Ag, and Ni) were selectively grown on the seed with their highly ordered arrangement by electroless plating. We studied the fabrication processes' suitability for control of the nanodot array size, as well as the plasmonic properties thereof.

Conjugated polymer chains confined in vertical nanocylinders of a block-copolymer film: preparation, characterization, and optoelectronic function.

Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains.

High-Performance Organic Energy-Harvesting Devices and Modules for Self-Sustainable Power Generation under Ambient Indoor Lighting Environments.

Organic photovoltaics (OPVs) that perform more efficiently under artificial indoor lighting conditions than they do under sunlight are attracting growing interest as they can potentially serve as ambient energy harvesters for powering low-power electronics and portable devices for the Internet of Things. Herein, solution-processed small-molecule OPVs are demonstrated to exhibit high power conversion efficiencies exceeding 16% under white LED illumination, delivering high output power densities of up to 12.4 and 65.3 µW cm-2 at 200 and 1000 lx, respectively. Increasing the open-circuit voltage ( Voc) of OPVs is a critical factor for achieving higher indoor photovoltaic performance. Toward real applications, this small-molecule OPV system is adopted to fabricate six series-connected modules with an active area of ∼10 cm2 that are capable of generating a high output power surpassing 100 µW and a high Voc of over 4.2 V even under dimly lit indoor conditions of 200 lx. These results indicate that OPVs are promising as indoor electric power sources for self-sustainable electronic devices.

Terahertz emission from gold nanorods irradiated by ultrashort laser pulses of different wavelengths.

Electron photoemission and ponderomotive acceleration by surface enhanced optical fields is considered as a plausible mechanism of terahertz radiation from metallic nanostructures under ultrafast laser excitation. To verify this mechanism, we studied experimentally terahertz emission from an array of gold nanorods illuminated by intense (~10-100 GW/cm2) femtosecond pulses of different central wavelengths (600, 720, 800, and 1500 nm). We found for the first time that the order of the dependence of the terahertz fluence on the laser intensity is, unexpectedly, almost the same (~4.5-4.8) for 720, 800, and 1500 nm and somewhat higher (~6.6) for 600 nm. The results are explained by tunneling currents driven by plasmonically enhanced laser field. In particular, the pump-intensity dependence of the terahertz fluence is more consistent with terahertz emission from the sub-cycle bursts of the tunneling current rather than with the ponderomotive mechanism.

High-Crystallinity π-Conjugated Small Molecules Based on Thienylene-Vinylene-Thienylene: Critical Role of Self-Organization in Photovoltaic, Charge-Transport, and Morphological Properties.

Narrow-band-gap small molecules with π-extended backbones are promising donor materials for solution-processed bulk-heterojunction (BHJ) organic solar cells (OSCs). Herein, a series of acceptor-donor-acceptor (A-D-A) photovoltaic small molecules incorporating thienylene-vinylene-thienylene (TVT) as a central D unit and alkyl-substituted rhodanine or 2-(1,1-dicyanomethylene)rhodanine as terminal A units are designed and synthesized. Their physical properties including photoabsorption, electronic energy levels, hole mobility, and morphological characteristics are systematically investigated. Using solvent vapor annealing (SVA), the morphologies of the BHJ photoactive layers composed of these small-molecule donors and a [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) acceptor can be properly modulated. As a result of increased crystallinity of the donors and desired phase segregation between the donors and PC71BM upon rapid SVA treatment, the photovoltaic performances of the resultant OSC devices undergo drastic enhancement. The results reported here indicate that high-efficiency small-molecule OSCs can be achieved through rational design of the TVT-based molecular framework and optimization of the nanoscale phase-segregated morphology via proper SVA treatment.

Transformation of Block Copolymer Nanoparticles from Ellipsoids with Striped Lamellae into Onionlike Spheres and Dynamical Control via Coupled Cahn-Hilliard Equations.

Annealing of block copolymers has become a tool of great importance for the reconfiguration of nanoparticles. Here, we present the experimental results of annealing block copolymer nanoparticles and a theoretical model to describe the morphological transformation of ellipsoids with striped lamellae into onionlike spheres. A good correspondence between the experimental findings and predictions of the model was observed. The model based on finding the steepest direction of descent of an appropriate free energy leads to a set of Cahn-Hilliard equations that correctly describe the dynamical transformation of striped ellipsoids into onionlike spheres and reverse onionlike particles, regardless of the nature of the annealing process. This universality makes it possible to describe a variety of experimental conditions involving nanoparticles underlying a heating process. A notable advantage of the proposed approach is that it enables selective control of the interaction between the confined block copolymer and the surrounding medium. This feature endows the model with a great versatility to enable the reproduction of several combined effects of surfactants in diverse conditions, including cases with reverse affinities for the block copolymer segments. A phase diagram to describe a variety of morphologies is presented. We employ the relationship between the temperature-dependent Flory-Huggins parameter and the width of the interfaces to account for changes in temperature due to the heating process. Simulation results correctly show how the transformation evolves as the temperature increases. This increment in temperature corresponds to progressively smaller values of the interfacial width. We anticipate that the proposed approach will facilitate the design and more precise control of experiments involving various kinds of annealing processes.

Oligothiophene-Indandione-Linked Narrow-Band Gap Molecules: Impact of π-Conjugated Chain Length on Photovoltaic Performance.

Solution-processed organic solar cells (OSCs) based on narrow-band gap small molecules hold great promise as next-generation energy-converting devices. In this paper, we focus on a family of A-π-D-π-A-type small molecules, namely, BDT- nT-ID ( n = 1-4) oligomers, consisting of benzo[1,2- b:4,5- b']dithiophene (BDT) as the central electron-donating (D) core, 1,3-indandione (ID) as the terminal electron-accepting (A) units, and two regioregular oligo(3-hexylthiophene)s ( nT) with different numbers of thiophene rings as the π-bridging units, and elucidate their structure-property-function relationships. The effects of the length of the π-bridging nT units on the optical absorption, thermal behavior, morphology, hole mobility, and OSC performance were systematically investigated. All oligomers exhibited broad and intense visible photoabsorption in the 400-700 nm range. The photovoltaic performances of bulk heterojunction OSCs based on BDT- nT-IDs as donors and a fullerene derivative as an acceptor were studied. Among these oligomers, BDT-2T-ID, incorporating bithiophene as the π-bridging units, showed better photovoltaic performance with a maximum power conversion efficiency as high as 6.9% under AM 1.5G illumination without using solvent additives or postdeposition treatments. These favorable properties originated from the well-developed interpenetrating network morphology of BDT-2T-ID, with larger domain sizes in the photoactive layer. Even though all oligomers have the same A-D-A main backbone, structural modulation of the π-bridging nT length was found to impact their self-organization and nanostructure formation in the solid state, as well as the corresponding OSC device performance.

Pyrimidine-based twisted donor-acceptor delayed fluorescence molecules: a new universal platform for highly efficient blue electroluminescence.

Deep-blue emitters that can harvest both singlet and triplet excited states to give high electron-to-photon conversion efficiencies are highly desired for applications in full-color displays and white lighting devices based on organic light-emitting diodes (OLEDs). Thermally activated delayed fluorescence (TADF) molecules based on highly twisted donor-acceptor (D-A) configurations are promising emitting dopants for the construction of efficient deep-blue OLEDs. In this study, a simple and versatile D-A system combining acridan-based donors and pyrimidine-based acceptors has been developed as a new platform for high-efficiency deep-blue TADF emitters. The designed pre-twisted acridan-pyrimidine D-A molecules exhibit small singlet-triplet energy splitting and high photoluminescence quantum yields, functioning as efficient deep-blue TADF emitters. The OLEDs utilizing these TADF emitters display bright blue electroluminescence with external quantum efficiencies of up to 20.4%, maximum current efficiencies of 41.7 cd A-1, maximum power efficiencies of 37.2 lm W-1, and color coordinates of (0.16, 0.23). The design strategy featuring such acridan-pyrimidine D-A motifs can offer great prospects for further developing high-performance deep-blue TADF emitters and TADF-OLEDs.

Thermally Activated Delayed Fluorescence Polymers for Efficient Solution-Processed Organic Light-Emitting Diodes.

Thermally activated delayed fluorescence (TADF) π-conjugated polymers are developed for solution-processed TADF-OLEDs. Benzophenone-based alternating donor-acceptor structures contribute to the small ∆EST , enabling efficient exciton-harvesting through TADF. Solution-processed OLEDs using the TADF polymers as emitters can achieve high maximum external electroluminescence efficiencies of up to 9.3%.

Linear assembly of a porphyrin-C60 complex confined in vertical nanocylinders of amphiphilic block copolymer films.

Linear assemblies of a 1 : 1 porphyrin-fullerene C60 complex were formed in vertical cylindrical polyether nanodomains of amphiphilic block copolymer films by a simple spin coating-annealing method. The nanocylinder structures were retained even with high contents of the complex in the polymer films.

Transition-metal-free controlled polymerization for poly(p-aryleneethynylene)s.

A transition-metal-free controlled polymerization for the attainment of poly(p-aryleneethynylene)s is developed. The polymerization of 1-pentafluorophenyl-4-[(trimethylsilyl)ethynyl]benzene with a catalytic amount of fluoride anions proceeds in a chain-growth-like manner to afford polymers with controlled molecular weights and low polydispersity indexes. The mechanism involves a pentacoordinated fluorosilicate as a key intermediate. The anionic "living" nature of this process is applied to block copolymerization and also surface-terminated polymerization.

Single-molecule electroluminescence and photoluminescence of polyfluorene unveils the photophysics behind the green emission band.

Optoelectronic properties of polyfluorene, a blue light-emitting organic semiconductor, are often degraded by the presence of green emission that originates mainly from oxidation of the polymer. Here, we use single-molecule electroluminescence (EL) and photoluminescence (PL) spectroscopy on polyfluorene chains confined in vertical cylinders of a phase-separated block copolymer to spectrally resolve the green band and investigate in detail the photophysical processes responsible for its appearance. In both EL and PL, a substantial fraction of polyfluorene chains shows spectrally stable green emission which is ascribed to a keto defect. In addition, in EL, we observe a new type of vibrationally resolved spectra distributed over a wide range of frequencies and showing strong spectral dynamics. Based on quantum chemical calculations, this type is proposed to originate from charge-assisted formation and stabilization of ground-state aggregates. The results are expected to have broad implications in the fields of photophysics and material design of polyfluorene materials.