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Multicomponent supramolecular assembly systems enable the generation of materials with outstanding properties, not obtained from single-component systems, via a synergetic effect. Herein, we demonstrate a novel supramolecular coassembly system rendering highly ordered quantum dot (QD) arrangement structures formed via the self-assembly of azobenzene derivatives, where the photocontrollable photoluminescence (PL) properties of the QDs are realized based on photoisomerization. Upon mixing the assembled azobenzene derivatives and QDs in apolar media, a time-evolution coaggregation into hierarchical nanosheets with a highly ordered QD arrangement structure occurs. Upon photoirradiation, the nanosheets transform into ill-defined aggregates without arranged QDs together with enhancing the PL intensity. In days, the photoirradiated coaggregates undergo recovery of the PL properties corresponding to the arranged QDs through thermal isomerization.

Here, we report the solvent dependence of the photoinduced anion exchange reaction of cesium lead halide perovskite nanocrystals (NCs) in solutions containing halomethane solvents such as CHCl3. Th...

Inorganic cesium lead halide perovskite nanocrystals (PNCs) are gaining attention due to their remarkable optical and electronic properties. However, because of their ionic properties, PNCs are uns...

Photoluminescence (PL) on/off switching systems using photochromic molecules have a high potential for a wide range of applications, such as optical memories, chemo- and biosensing, and superresolu...

Cesium lead halide perovskite nanocrystals are widely studied as among the most attractive emissive nanomaterials because of their high photoluminescence quantum yield and tunable emission wavelengths over the whole visible-light region by the halide ion-exchange reaction. However, the reactions were often observed in solution and generally very fast, which interferes with the fine-tuning capability of the emission properties. Here, we report a novel nanocrystal-organogel hybrid soft material in which the perovskite nanocrystals in a supramolecular gel exhibit extremely slow and inhomogeneous anion-exchange reactions that are different from those in solution. Furthermore, the inhomogeneous emission in the gel became homogeneous over several days due to a slow diffusion.

Colloidal semiconductor nanocrystals, known as quantum dots (QDs), are regarded as brightly photoluminescent nanomaterials possessing outstanding photophysical properties, such as high photodurability and tunable absorption and emission wavelengths. Therefore, QDs have great potential for a wide range of applications, such as in photoluminescent materials, biosensors and photovoltaic devices. Since the development of synthetic methods for accessing high-quality QDs with uniform morphology and size, various types of QDs have been designed and synthesized, and their photophysical properties dispersed in solutions and at the single QD level have been reported in detail. In contrast to dispersed QDs, the photophysical properties of assembled QDs have not been revealed, although the structures of the self-assemblies are closely related to the device performance of the solid-state QDs. Therefore, creating and controlling the self-assembly of QDs into well-defined nanostructures is crucial but remains challenging. In this Minireview, we discuss the notable examples of assembled QDs such as dimers, trimers and extended QD assemblies achieved using organic templates. This Minireview should facilitate future advancements in materials science related to the assembled QDs.

Most azobenzene derivatives are utilized as well-defined photoresponsive materials, but their emission properties have not been of great interest as they are relatively poor. Here, we report crystallization-induced emission (CIE) based on the suppression of the photoisomerization of azobenzene derivatives. Although these molecules show negligible emission in solution, their microcrystals exhibit intense emission from the azobenzene moieties as a result of CIE. Upon rapid precipitation, fine particles with low crystallinity were kinetically formed and underwent CIE over time with a concomitant increase in crystallinity. Furthermore, we demonstrated "photocutting" of an emissive single crystal using a strong laser by a combination of CIE behavior and photomelting based on the photoisomerization of the azobenzene moiety. Our results regarding the CIE behavior of azobenzene derivatives in addition to their photoisomerization can provide a new platform for developing photoresponsive luminescent materials.

Supramolecular assemblies have been extensively studied because of their fundamental insights into intermolecular interactions and their potential applications to optoelectronic devices. Among vari...

The formation of well-defined nanostructures comprising assembled semiconductor quantum dots (QDs) is a challenging research task. Recently, we found that the introduction of π-conjugated molecules...

The photo-induced generation of unstable molecules generally requires stringent conditions to prevent oxidation and the concomitant decomposition of the products. The visible-light-induced conversion of two heptacene precursors to heptacene was studied. Single crystals of bis- and mono-α-diketone-type heptacene precursors (7-DK2 and 7-DK1, respectively), were prepared to investigate the effect of precursor structure on reactivity. The photoirradiation of a 7-DK2 single crystal cleaved only one α-diketone group, forming an intermediate bearing a pentacene subunit, while that of a 7-DK1 single crystal gave rise to characteristic absorption peaks of heptacene and their increase in intensity with photoirradiation time, indicating the generation of heptacene without decomposition. Heptacene production was not observed when the precursors were photoirradiated in solution, implying that the single crystal interior provided isolation from the external environment, thus preventing heptacene oxidation.

Recently, we revealed that 6,13-dihydro-6,13-ethanopentacene-15,16-dione (PDK) could be quantitatively photoconverted into pentacene even in the crystal phase, accompanied by the destruction of the crystals. In this work, we investigated the relationship between the photoinduced morphological changes and the light intensity for the photoconversion at a single micrometre-sized crystal level. Photoirradiation with a strong intensity (over 100 kW cm-2) resulted in hole formation in a single crystal. When medium intensity (0.5-100 kW cm-2) was irradiated, destruction including separation and jumping of the crystal was observed. Absorption spectrum measurement of the single crystal revealed that when almost same number of pentacene was generated, the destruction was induced by the generated strain within crystal due to the stacking mismatch between the different molecules. Upon photoirradiation with a low intensity (below 0.5 kW cm-2), protruding pillar objects were observed on the crystal surface. This formation is a result of the surface movement of molecules through the relaxation of strain. Our results provide important insight into stimuli-responsive crystal materials and could contribute to the generation and application of remotely controllable smart materials.

Colloidal semiconductor nanocrystals, so-called quantum dots (QDs), are attractive as molecular-like smart nanomaterials, and their emission and optoelectronic properties in the dispersed state have been actively studied. The construction of supramolecular structures composed of multiple QDs, however, is still challenging. Here, a new strategy to form supramolecular QD structures via self-assembly of perylene bisimide (PBI) dyes is demonstrated. In a mixed solution, QDs and PBI undergo time-dependent fusion to form an isolated colloidal QD-PBI complex or a unique QD-PBI co-aggregate composed of QDs arranged along a sheet-like PBI nanostructure, and these dramatically different supramolecular structures can be controlled by the solvent polarity.

Recently organic–inorganic lead-halide perovskite nanoparticles (NPs) have been attractive as low-cost and high-conversion-efficient solar cells and light-emitting diode. The generation of the exciton and dissociation into free carriers are quite important for primary photoelectric conversion processes. In this study, we have examined the initial exciton dynamics of CH3NH3PbBr3 (MAPbBr3) NPs by femtosecond transient absorption spectroscopy and picosecond time-resolved luminescence spectroscopy. The ultrafast exciton quenching with a time constant of 200 fs was observed, which may be related with longitudinal optical phonon and/or lurching motion of MA cation in the excited state. In addition, higher electronic state with a short lifetime was clearly detected by the excitation intensity dependence of time-resolved luminescence and transient absorption spectra. These findings of MAPbBr3 NPs are very important not only for understanding the generation of charge carrier but also for constructing the high-effi...

The generation of surface-enhanced Raman scattering (SERS) was directly observed in situ during the fabrication of Ag nanoparticle (AgNP) dimers and trimers using atomic force microscopy (AFM) manipulation, and the size of the SERS hot spot was estimated using the super-resolution imaging technique. SERS from 4,4’-bipyridine was observed upon the fabrication of the AgNP dimers and trimers using AFM manipulation. Then, the SERS spots were analyzed by fitting with the point spread function for super-resolution imaging. The distribution of the centroid position of the SERS spot from the AgNP dimer was 9 nm along the x-axis and 8 nm along the y-axis, which represent the size of the SERS hot spot. The same technique was applied to the AgNP trimer. The obtained results are important not only for the SERS technique but also for other plasmon enhancement techniques which are useful in a wide range of research areas.

Emission photon statistics, i.e., single-photon and multi-photon emissions, of isolated QDs is required for tailoring optoelectronic applications. In this article, we demonstrate that the emission photon statistics can be modified by the control of the spectral overlap of the QDs with the localized surface plasmon resonance (LSPR) of the metal nanoparticle (metal NP) and by the distance between the QD and the metal NP. Moreover, the contribution to the modification of the emission photon statistics, which is the excitation and emission enhancements and the quenching generated by the spectral overlap and the distance, is elucidated. By fabricating well-defined SiO2-coated AgNPs and AuNPs (metal/SiO2), the spectral overlap originated from the metal species of Ag and Au and the distance constituted by the thickness of the SiO2 shell are controlled. The probability of single-photon emission of single QD was increased by the enhancement of the excitation rate via adjusting the distance using Ag/SiO2 while the single-photon emission was converted to multi-photon emission by the effect of exciton quenching at a short distance and a small spectral overlap. By contrast, the probability of multi-photon emission was increased by enhancement of the multi-photon emission rate and the quenching via the spectral overlap using Au/SiO2. These results indicated the fundamental finding to control emission photon statistics in single QDs by controlling the spectral overlap and the distance, and understand the interaction of plasmonic nanostructures and single QD systems.

The enhancement of multiphoton emission from a single colloidal nanocrystal quantum dot (NQD) interacting with a plasmonic nanostructure was investigated using SiO2-coated silver nanoparticles (Ag/SiO2) as the plasmonic nanostructure. Using Ag/SiO2 with five different SiO2 shell thicknesses, we observed modification of the emission behavior depending on the distance between the NQD and silver nanoparticle (AgNP). The single-photon emission from a single NQD converted to multiphoton emission with a shortening of the emission lifetime as the NQD–AgNP distance decreased, whereas an increase and decrease in the emission intensity were observed. From the distance-dependent results, we concluded that the probability of multiphoton emission was increased by the quenching of the single-exciton state due to energy transfer from the NQD to the AgNP and that the emission intensity was modified by the enhancement of the excitation rate and quenching. These results indicate that the plasmonic nanostructure is very eff...

Hot carrier transfer of semiconductor nanocrystals (NCs) plays an important role for solar energy conversion. In this chapter, effects of quantum confinement of colloidally synthesized semiconductor NCs on hot carrier transfer and the carrier transfer mechanism are discussed on the basis of state-selective excitation of femtosecond transient absorption spectroscopy and initial bleach yield of band-edge state. The role of phonon emission from higher excited states on hot carrier transfer in quantum-confined NCs is revealed. In addition, carrier manipulation of a single semiconductor NC by plasmonic nanostructures is demonstrated with single particle spectroscopy. The distance dependence between a single semiconductor quantum dot (QD) and a plasmonic nanostructure on luminescence intensity and lifetime of a single semiconductor QD is discussed in terms of the electromagnetic enhancement of absorption and luminescence and energy transfer quenching by the plasmonic nanostructure.

Postsynthesis anion-exchange reaction of cesium lead halide (CsPbX3; X = Cl, Br, and I) perovskite nanocrystals (NCs) has emerged as a unique strategy to control band gap. Recently, the partially a...

The enhancement of multiphoton emission from a single colloidal nanocrystal quantum dot (NQD) interacting with a plasmonic nanostructure was investigated using a silver-coated atomic force microscopy tip (AgTip) as the plasmonic nanostructure. Using the AgTip, which exhibited a well-defined localized surface plasmon (LSP) resonance band, we controlled the spectral overlap and the distance between the single NQD and the AgTip. The emission behavior of the single NQD when approaching the AgTip at the nanometer scale was measured using off-resonance (405 nm) and resonance (465 nm) excitation of the LSP. We directly observed the conversion of the single-photon emission from a single NQD to multiphoton emission with reduction of the emission lifetime at both excitation wavelengths as the NQD-AgTip distance decreased, whereas a decrease and increase in the emission intensity were observed at 405 and 465 nm excitation, respectively. By combining theoretical analysis and the numerical simulation of the AgTip, we deduced that the enhancement of the multiphoton emission was caused by the quenching of the single-exciton state due to the energy transfer from the NQD to the AgTip and that the emission intensity was increased by enhancement of the excitation rate due to the electric field of the LSP on the AgTip. These results provide evidence that the photon statistics and the photon flux from the single NQD can be manipulated by the plasmonic nanostructure through control of the spectral overlap and the distance.

The additive effect on small-molecule-based p–i–n-type devices has been little investigated so far. We focus on the improvement of the miscibility of tetrabenzoporphyrin (BP) and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) blend film by addition of fullerene-linked tetrabenzoporphyrin (BP–C60) as an additive to the interlayer (i-layer). BP is one of the most promising p-type organic semiconductors, and BP films can be prepared readily by heating as-cast films of the precursor (a bicyclo[2.2.2]octadiene-fused porphyrin; CP), that results in changes from amorphous CP films to polycrystalline BP films. Because of the high crystallinity of BP, large BP grains on the scale of tens to hundreds of nanometers are generated in blend films of BP and PC61BM during film fabrication. We found that the addition of BP–C60 as an additive (3, 5, 7, and 10 wt%) to the i-layer composed of BP and PC61BM improves the miscibility of BP and PC61BM. The power conversion efficiency of p–i–n-type organic solar cells consisting of a blend film of BP and PC61BM (i-layer) sandwiched by BP (p-layer) and PC61BM (n-layer) improved by up to 50% as compared to that of a control device after the addition of BP–C60 to the i-layer. The film morphology was investigated using atomic force microscopy, fluorescence microspectroscopy, two-dimensional grazing-incident wide-angle X-ray diffraction measurements, and scanning electron microscopy. Interacting with both BP and PC61BM, the addition of BP–C60 led to changes in the grain size as well as an increase in the size of the BP/PC61BM interface and hence effective charge separation in the p–i–n device. This morphological improvement is attributable to the ability of BP–C60, which exhibits the characteristics of both BP and C60, to promote the compatibility of BP and PC61BM. This study is a significant step towards the development of high-performance p–i–n-type solar cells and should pave the way for the fabrication of high-performance bulk-heterojunction layers in solution-processed organic photovoltaic devices.

The change of photon statistics in the fluorescence of a single CdSe/ZnS core/shell colloidal nanocrystal quantum dot (NQD) accompanying the atomic force microscopy (AFM) manipulation of a cubic Au nanoparticle (AuCube) was investigated to elucidate the effect of plasmonic nanostructures on the multiexciton dynamics of the NQD. Upon coupling to an AuCube of a well-defined size and shape, we directly observed the conversion of a single-photon emission from an individual NQD to a multiphoton emission, and this was accompanied by an increase in fluorescence intensity and a reduction in fluorescence lifetime. The multiphoton emission then returned to a single-photon emission upon separating the AuCube from the single NQD. The efficiency of the multiphoton emission was enhanced 6.9 times through the use of the AuCube. The enhancement of the multiphoton emission was attributable mainly to the augmentation of the biexciton emission rate. These results provide evidence that quantum dot photon statistics can be ma...

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 [times] 10-6 and 8.1 [times] 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.

The enhancement of multiphoton emission from a single colloidal nanocrystal quantum dot (NQD) interacting with a plasmonic nanostructure was investigated using SiO2-coated silver nanoparticles (Ag/SiO2) as the plasmonic nanostructure. Using Ag/SiO2 with five different SiO2 shell thicknesses, we observed modification of the emission behavior depending on the distance between the NQD and silver nanoparticle (AgNP). The single-photon emission from a single NQD converted to multiphoton emission with a shortening of the emission lifetime as the NQD–AgNP distance decreased, whereas an increase and decrease in the emission intensity were observed. From the distance-dependent results, we concluded that the probability of multiphoton emission was increased by the quenching of the single-exciton state due to energy transfer from the NQD to the AgNP and that the emission intensity was modified by the enhancement of the excitation rate and quenching. These results indicate that the plasmonic nanostructure is very effective in controlling the emission photon statistics, that is, single- and multi-photon emission and the emission intensity from the single NQD, which is difficult to achieve in an NQD alone.

Emission photon statistics, i.e., single-photon and multi-photon emissions, of isolated QDs is required for tailoring optoelectronic applications. In this article, we demonstrate that the emission photon statistics can be modified by the control of the spectral overlap of the QDs with the localized surface plasmon resonance (LSPR) of the metal nanoparticle (metal NP) and by the distance between the QD and the metal NP. Moreover, the contribution to the modification of the emission photon statistics, which is the excitation and emission enhancements and the quenching generated by the spectral overlap and the distance, is elucidated. By fabricating well-defined SiO

We have fabricated well-defined nanostructures such as SiO2-coated Ag nanoparticles (NPs) connected with quantum dots (QDs) (Ag/SiO2-QDs) so as to control the fluorescence enhancement induced by localized surface plasmon resonance. Namely, the distance between Ag NP and QD should be noted as a controllable model to investigate the fluorescence enhancement effect. Actually, highly monodispersed Ag NP as a core was first coated with five thicknesses of SiO2 as a shell, and then QDs were specifically adsorbed onto the surface of the amino-functionalized SiO2-coated Ag NPs. As a result, the fluorescence intensity increased with the shell thickness as a result of excitation enhancement. On the other hand, the fluorescence intensity decreased when the shell thickness became thinner because of the induced quenching. Therefore, the distance between Ag NPs and QDs should be optimized to control and enhance the fluorescence intensity.

The photon antibunching behavior in the photoluminescence (PL) of single CdSe/ZnS semiconductor nanocrystals (NCs) interacting with the localized surface plasmon resonance (LSPR) of Ag nanostructure was investigated using fs-pulsed laser excitation at two excitation wavelengths. The time traces of the PL intensity, the PL decay curves, and the photon correlations of single NCs on a rough Ag film and on a coverslip were measured simultaneously, and an increase in the PL intensity accompanied by shortening of the PL lifetime was observed for the single NCs on the rough Ag film. The enhancement factor of the PL intensity depended on the excitation wavelength. Nearly all of the single NCs with enhanced PL exhibited photon antibunching behavior independent of the enhancement factor. Based on the enhanced radiative- and nonradiative-decay rates estimated from the experimental data, the mechanism of the photon antibunching behavior was considered as follows. To exhibit the photon antibunching behavior, the nonradiative Auger recombination between the generated excitons in a single NC is important. When the radiative- and the nonradiative-decay rates enhanced by the LSPR are faster than the Auger recombination rate, the probability of photon antibunching decreases. However, such fast radiative- and the nonradiative decay rates were not observed for single NCs interacting with the LSPR of the rough Ag film in this work. Therefore, the PL intensity from a single NC can be increased while maintaining the photon antibunching behavior. Our findings assist in the creation of effective single-photon sources and provide important information on the emission properties of an NC coupled with the plasmon of a metal nanostructure.

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.

Extremely pure polymer matrices were used for elucidating the fluorescence properties of singly isolated charge-transfer (CT) complexes formed between the donor N-ethylcarbazole and the acceptor 1,2,4,5-tetracyanobenzene. Simultaneous measurements (time traces of CT fluorescence intensities and lifetimes) using single-molecule fluorescence spectroscopy showed three patterns: (1) fluctuations in the fluorescence intensities and lifetimes seldom occurred, (2) the fluorescence intensities frequently fluctuated together with the lifetimes, or (3) in addition to the above fluctuations with time, blinking and/or off-states longer than 1 s were observed. For methacrylate polymers, both the degree of fluctuations in the CT fluorescence lifetimes and the percentage of the CT complexes showing off-states increased with the free volume of the host polymers. These results suggest that the degree of fluctuations in the relative geometrical arrangements of the donor and acceptor molecules is related to the availability of space in the host polymer, and that the free volume provides the necessary space for formation of non-fluorescent donor–acceptor geometries of the CT complexes and/or temporal dissociation of the CT complexes. Survival times of the CT fluorescence were also closely related with the free volume of the host polymers.

To reveal the exciton dynamics, particularly multiexciton dynamics in single colloidal CdSe/ZnS quantum dots (QDs) interacting with the localized surface plasmon resonance (LSPR) of silver nanoparticles (AgNPs), we investigated the single-photon emission behavior in the fluorescence from the single QDs using a single-molecule spectroscopy technique in combination with a femtosecond-pulsed laser excitation. By applying simultaneous measurements of the photon-correlation (photon antibunching), the fluorescence intensity, and the fluorescence lifetime to the single QD near AgNPs, we revealed that the probability of single-photon emission strongly depended on the fluorescence lifetime; that is, the probability of single-photon emission decreased when the lifetime was shorter than subnanoseconds. On the basis of the estimation of both radiative and nonradiative decay rates enhanced by the LSPR, the following mechanism was suggested. In the absence of AgNPs, multiple excitons generated by a high-power excitatio...

Single molecule fluorescence spectroscopy (SMS) was used to elucidate the fluorescence dynamics of singly isolated charge-transfer (CT) complexes formed between various monocarbazolyl and dicarbazo...

Single-photon behavior in the emission from a single nanoparticle consisting of a single poly[2-methoxy-5-(2′-ethylhexyloxy)- p -phenylene vinylene] (MEH-PPV, molecular weight: 2,600,000 amu) chain has been investigated. Photon correlation measurements of a number of single nanoparticles revealed that the probability of single-photon emission from the single nanoparticles clearly increases, compared with that of single chains embedded in host polymer matrices, poly(methyl methacrylate) (PMMA) and polystyrene (PS). The result suggested that even a single MEH-PPV chain with high molecular weight, which does not exhibit single-photon emission in PMMA and PS, is forced to exhibit single-photon emission by adopting “compact” chain conformation like nanoparticle. Efficient exciton migration and exciton annihilation processes in the compact chain conformation most probably result in the efficient single-photon emission from the single nanoparticle. The present results indicate that multi-quantum systems consisting of a large number of chromophores, such as the MEH-PPV, can be made to behave as single-photon sources by appropriately controlling their size.

In recent experiments, the signal-to-noise ratio and the photon pair correlation are measured simultaneously by improving the Hanbury-Brown and Twiss method. We show that judgement on whether the background noise obeys Poisson statistics or not is possible from the data of such measurements. If the background is subject to Poisson statistics, the results of both measurements enable to estimate the photon pair correlation in the absence of noise from that measured under background noise. The method is useful to remove the effect of background noise from the photon correlation measured by exciting multichromophore systems. We also show that the normalized photon pair correlation is not necessarily zero in the absence of background noise when single photon is emitted from multiple excitons as a result of the competition among the pair annihilation, and the unimolecular nonradiative and radiative processes.

4-Cyano-4′-(1-(1-pyrenyl)- n -octyloxy)biphenyl (8OCBPy), where the hydrogen atom of a well-known mesogen 4-cyano-4′- n -octyloxybiphenyl (8OCB) is substituted with one pyrenyl (Py) chromophore, was synthesized. When 8OCBPy was doped in the mesophases of the similar mesogen of 4-cyano-4′- n -decyloxybiphenyl (10OCB), the Py chromophores should be oriented by a constraint in the mesophases as compared with free chromophores dispersed in the mesophases. The binary mixture exhibited smectic A (Sm A) and nematic (N) mesophases. The mesophases and isotropic (I) phase of the binary mixture exhibited excimer as well as monomer fluorescence. The intermolecular excimer formation-dissociation kinetics of 8OCBPy in the Sm and I phases of its binary mixture was investigated in comparison with that for a 1-ethylpyrene binary system. Positive enthalpy and entropy changes for the excimer formation were found in the Sm A mesophase, whereas their usual changes were found in the I phase. These anomalous phenomena observed in the Sm A mesophase were interpreted by the entropy-controlled excimer formation associated with the decrease in ordering of the 10OCB-mesogen molecules around the 8OCBPy arranged in the Sm A layers.

We report the photoluminescence properties of polymer alternating multilayer films containing a fluorescent dye in one component. The alternating multilayer film with periodicity in both refractive indices and dye distribution showed 6 times higher intensity of amplified spontaneous emission than the multilayer film with periodicity in dye distribution only. Multilayer films that have a structure of Fabry–Perot resonator showed a lasing threshold of approximately 1.7 mJ cm − 2 .

We prepared nanoparticles of an organic dye, acridine orange (AO), dispersed in poly(methacrylic acid) (PMA) films by spin-coating the solution of the two components. The surface of the AO/PMA films became bumpier with increasing AO concentration (cAO). The absorption and fluorescence spectra of AO/PMA films exhibited a marked dependence on cAO at low cAO (cAO 2.1 × 10− 1 mol kg− 1). The peak shift of fluorescence spectra with changing cAO was as large as ∼ 100 nm.

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.