Sadahiro Masuo

Photofabrication of Fullerene-Shelled Quantum Dots Supramolecular Nanoparticles for Solar Energy Harvesting

Quantum dots-based electron donor-acceptor systems play a rising role in the design of renewable and carbon-free energy harvesting technologies. In this article, we discuss the photofabrication of fullerene-shelled quantum dots supramolecular nanoparticles, in which the fullerene shell acts as not only a well-defined electron acceptor but also a robust protecting layer against the photocorrosion of the quantum dot core. We evaluate the ensemble and single-molecule electron transfer from the core to the shell in the nanoparticles and the photocurrent response of a photoelectrochemical cell constructed using the nanoparticles. The supramolecular nanoparticle has been prepared by the covalent tethering of a fullerene-thiol monolayer to the quantum dot followed by the photochemical reactions of free fullerene-thiol to the tethered monolayer. The nanoparticles are characterized using scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Correlated single-photon emission and the two-state ON-OFF photoluminescence show that single quantum dots are included in the supramolecular nanoparticles. The fullerene-shells suppress the blinking of single quantum dots by acting as well-defined electron traps, without allowing the transfer of Auger electrons to unknown traps. Electron transfer from the quantum dot-core to the fullerene-shell is apparent from the short ON and OFF durations in the photoluminescence intensity trajectories of single quantum dots, quenching of the photoluminescence intensity and lifetime of quantum dots at the ensemble level, and the characteristic transient absorption band of the anion radical of fullerene. We next construct a photoelectrochemical cell using the supramolecular nanoparticles, and the transferred electron is externally driven in the cell to generate ∼400 μA/cm(2) photocurrent. Electron transfer from the highly stable quantum dots to the protecting fullerene-shells places the supramolecular nanoparticles among the most promising antenna systems for the construction of cost-effective and stable next generation solar energy harvesting systems.

Photon statistics in enhanced fluorescence from a single CdSe/ZnS quantum dot in the vicinity of silver nanoparticles

Single-photon emission behavior in the enhanced fluorescence from single colloidal quantum dots (QDs) near silver nanoparticles (AgNPs) was investigated using a single molecule fluorescence spectroscopy technique. It was found that the degree of fluorescence enhancement from single QDs with AgNPs increased with decrease in the lifetime and the probability of single-photon emission, that is, highly enhanced fluorescence with a shortened lifetime exhibited a low probability of single-photon emission. The present results yield new insights into fundamentals of QD-metal nanostructure interactions, and are also important to understand the mechanism of the fluorescence enhancement by localized surface plasmon of metal nanostructures.

Photon Antibunching in the Emission from a Single Organic Dye Nanocrystal

We demonstrated that the emission from a single organic nanocrystal consisting of organic dye molecules shows photon antibunching. That is, an assembling structure consisting of many chromophores can also be made to behave as a single-photon source by controlling the size. We found that most of single nanocrystals within a size range from 35 to 85 nm show photon antibunching even when more than one exciton in a crystal is generated by an intense single excitation pulse. On the other hand, single micrometer-sized crystals showed no antibunching. The present results indicate that molecular assemblies can also be considered as candidates for new single-photon sources.

Nanoparticle Formation of Pentacene by Laser Irradiation in Ethanol Solution

Laser irradiation using a Nd3+:YAG laser (532 nm, 8 ns, 10 Hz) on an ethanol suspension of micrometer-sized pentacene crystals induced absorption spectral changes in the solution, as a result of the formation of pentacene nanoparticles. The nanoparticles were platelike crystals. The nanoparticles formed by irradiation with a fluence of 50 mJ/cm2 for 30 min were 4–13 nm in height and 10–70 nm in width. The threshold laser fluence for the formation was determined to be ca. 20 mJ/cm2, and irradiation with fluences above 80 mJ/cm2 induced the decomposition of the pentacene nanoparticles. The nanoparticle size decreased with an increase in the laser fluence, which was reflected in the longest-wavelength peak position of the absorption bands of the pentacene nanoparticles. On the basis of these results, the mechanism of pentacene nanoparticle formation by laser irradiation is discussed in connection with those of vanadyl phthalocyanine and quinacridone systems reported by Masuhara and coworkers [J. Phys. Chem. A 106 (2002) 2135; Jpn. J. Appl. Phys. 42 (2003) 2725; Jpn. J. Appl. Phys. 45 (2006) 384].

Influence of molecular weight and conformation on single-photon emission from isolated conjugated polymer chains

The influence of molecular weight (MW) and chain conformation on single-photon emission from isolated chains of poly[2-methoxy,5-(2′-ethylhexyloxy)-p-phenylene-vinylene] have been investigated. The probability of single-photon emission clearly increased with decreasing MW, and when the polymer chains adopted the “collapsed” conformation, this probability was larger than for the “extended” conformation. Even single polymer chains of high MW behaved as single-photon sources by adopting the collapsed conformation. These results indicate that multi-quantum systems consisting of a large number of chromophores can be made to behave as single-photon sources by appropriately controlling their size.

Single Photon Emission from a Dendrimer Containing Eight Perylene Diimide Chromophores

A novel dendrimer containing eight perylene diimide chromophores has been synthesized and studied by ensemble and single-molecule spectroscopic techniques. Photon anti-bunching (coincidence) measurements on single molecules embedded in zeonex polymer films show that the dendrimer behaves as a deterministic (triggered) single photon source with only one fluorescence photon being emitted following pulsed laser excitation, even when more than one chromophore is excited. This behaviour is due to efficient singlet–singlet annihilation being operative in this dendrimer. Preliminary results indicate that the triplet lifetime and yield for this molecule are similar to the values for a molecule containing a single perylene diimide chromophore.

Side-chain engineering in a thermal precursor approach for efficient photocurrent generation

An ideal active-layer compound for bulk-heterojunction (BHJ) organic photovoltaic devices (OPVs) can assemble upon deposition to form the effective π–π stacking that facilitates exciton diffusion and charge-carrier transport. It is also expected to possess high-enough miscibility for forming sufficient heterojunctions to ensure efficient charge separation. However, these characteristics are often not compatible in organic small-molecule semiconductors: compounds endowed with rich self-π–π interaction capacity tend to be poor in miscibility, or maybe even insoluble in extreme cases. Herein, we postulate that a thermal precursor approach can serve as a way out of this dilemma, provided that molecules are properly engineered. This work evaluates a series of diketopyrrolopyrrole (DPP)–tetrabenzoporphyrin (BP) conjugates named Cn-DPP–BP (n = 4, 6, 8 or 10 depending on the length of alkyl groups on the DPP unit) as a p-type material in BHJ OPVs. These compounds are strongly aggregating and insoluble, thus processed via the thermal precursor approach in which the corresponding soluble derivatives (Cn-DPP–CP) are solution-processed into thin films and then converted to the target materials by in situ thermal reactions. The comparative study shows that the short-circuit current density largely depends on the length of alkyl substituents, ranging from 0.88 mA cm−2 with C10-DPP–BP to 15.2 mA cm−2 with C4-DPP–BP. Investigation into the structure of active layers through fluorescence-decay analysis, atomic-force microscopy, and two-dimensional grazing-incidence wide-angle X-ray diffractometry indicates that the introduction of shorter alkyl chains positively affects the miscibility and molecular orientation in BHJ layers. This trend is not fully parallel to those observed in the BHJ systems prepared through conventional solution techniques, and will provide a unique basis for devising a new class of high-performance OPV materials.

Synthesis and optical reactivity of 6,13-α-diketoprecursors of 2,3,9,10-tetraalkylpentacenes in solution, films and crystals

Tetraalkylpentacenes having alkyl chains at 2,3,9,10-positions (Et-PEN, Pr-PEN and Hex-PEN) were prepared from their precursors Et-PDK, Pr-PDK and Hex-PDK, respectively. Photoreactions proceeded both in solutions, thin-films, and crystals, thus the properties of Et-PDK in films can be studied despite the instability of the pentacenes in solution. Et-PEN showed significantly different aggregation-nature compared with the parent pentacene. The hole mobilities of Et-PEN and Pr-PEN in films were 3.4 × 10−6 and 8.1 × 10−7 cm2 V−1 s−1, respectively, determined by space-charge-limited current measurement, comparable with the order 10−6 cm2 V−1 s−1 of the electron mobility of Alq3.

Site-Selective Doping of Dyes into Polystyrene-block-Poly(4-vinyl pyridine) Diblock Copolymer Films and Selective Laser Ablation of the Dye-Doped Films

The site-selective doping of dyes into spin-cast thin films with different phase separation structures of polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP) diblock copolymers and the dopant-induced laser ablation of the dye-doped films fabricated were investigated. The selective doping of dyes into P4VP parts was carried out by immersing the films in a methanol solution containing the dyes, in which the driving force was induced by hydrogen bonds between the nitrogen atoms of pyridyl groups and the carboxylic groups of the dyes. Schematic models for the adsorption process of the dyes in the methanol solution were discussed. Dopant-induced laser ablation was carried out on the dye-doped block copolymer films, resulting in the ablation of dye-doped P4VP parts only. Factors affecting selective ablation, such as dyes, the morphologies of phase separation structures, the number-average molecular weights of the diblock copolymers, and irradiation environments, were discussed.

Application of Dopant-Induced Laser Ablation to Site-Selective Modification of Sea-Island Structures of Polystyrene-block-poly(4-vinylpyridine) Films

Dopant-induced laser ablation was applied to thin polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer films doped selectively with tetrakis(4-carboxyphenyl)porphine (TCPP) into the nanoscale spherical domain of P4VP-island parts. Under dry-film conditions, the ablation of the island parts was not induced. On the other hand, in methanol solvent, only the P4VP-island parts doped with TCPP were ablated selectively. The dopant-induced laser ablation is attributed to the fact that the P4VP-island parts are in the swollen state, where P4VP chains cross-linked by TCPP-dopant molecules exist with a high density in methanol. This is the first report concerning the site-selective laser ablation of diblock copolymer films.